Fungicidal pyrimidine compounds

ABSTRACT

The present invention relates to fungicidal pyrimidine compounds I, to their use and to methods for combating phytopathogenic fungi. The present invention also relates to seeds treated with at least one such compound. Furthermore the invention relates to processes for preparing compounds of formula I.

This application is a National Stage application of International Application No. PCT/EP2013/052008, filed Feb. 1, 2013, the entire contents of which is hereby incorporated herein by reference. This application also claims priority under 35 U.S.C. §119 to European Patent Application No. 12153760.9, filed Feb. 3, 2012; and European Patent Application No. 12154879.6, filed Feb. 10, 2012; the entire contents of which are hereby incorporated herein by reference.

The present invention relates to fungicidal pyrimidine compounds, to their use and to methods for combating phytopathogenic fungi. The present invention also relates to seeds treated with at least one such compound. Furthermore the invention relates to processes for preparing compounds of formula I.

WO 98/03272 A1 describes a process for the preparation of 4-amino-5-chloro-6-(1-fluoroethyl)pyrimidine compounds, which are pest controlling agents for agricultural and horticultural use. WO 97/28133 A1 discloses acylated 4-amino and 4-hydrazinopyrimidines and their use as pesticides. WO 95/18795 A1 relates to N-(4-pyrimidinyl)amide pesticides and EP 665225 A1 relates to 4-phenethylamino pyrimidine derivatives useful for chemical control of noxious organisms.

The compounds according to the present invention differ from those described in the abovementioned publications in that the pyrimidine ring carries a halogen substituent in 6-position and/or the specific linker X as defined herein.

EP 264217 A2 generally discloses certain aryl alkyl amino pyrimidine derivatives inter alia with fungicidal activity of formula:

EP 264217 A2 does not mention the specific combination of a halogen substituent in 6-position of the pyrimidine ring and the specific ethylene linker unit —X—CR¹R² as defined herein together with a heteroaryloxy substitution of the phenyl ring.

In many cases, in particular at low application rates, the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. This objective is achieved by the use of substituted pyrimidine compounds of formula I having good fungicidal activity against phytopathogenic harmful fungi.

Accordingly, the present invention relates to compounds of the formula I

wherein:

-   R^(a2), R^(a5) independently of each other, are hydrogen, halogen,     CN, NO₂, OH, SH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,     C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,     C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl,     C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,     C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-alkynyl,     C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,     C₃-C₈-cycloalkyloxy, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, NR^(A)R^(B),     C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″;     -   R^(A), R^(B) independently of each other are hydrogen,         C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, phenyl, benzyl,         C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl or —C(═O)—R′;     -   R′ is hydrogen, OH, NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl,         C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,         C₁-C₄-alkylamino or di(C₁-C₄-alkyl)amino;     -   R″ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl,         C₂-C₄-alkynyl or C₁-C₄-alkoxy-C₁-C₄-alkyl;     -   R′″ is hydrogen or C₁-C₄-alkyl; -   R^(a6) is halogen; -   R is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,     C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl,     C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,     C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, CN, CH₂CN, NR^(A)R^(B) or     CH₂—O—C(═O)R′; -   R¹, R² independently of each other are hydrogen, halogen, CN, OH,     C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,     C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl,     C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl,     C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy,     NR^(A)R^(B), C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein     the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4,     or 5 substituents selected from the group consisting of CN, halogen,     C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,     (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or     -   two radicals R¹ and R² that are bound to the same carbon atom         form together with said carbon atom a saturated or partially         unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a         saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered         heterocycle, wherein the ring member atoms of the abovementioned         heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms         selected from the group of N, O and S, and wherein the         abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4         substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl,         C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of         the abovementioned cycles may be respectively replaced by one or         two C(═O) or C(═S) groups; -   X is a divalent group selected from —CR³R⁴—, —C(═NR^(D))— and     —C(═NOR^(D))—, wherein     -   R^(D) is hydrogen or C₁-C₄-alkyl, and wherein     -   R³ and R⁴ independently of each other are hydrogen, CN,         C₁-C₄-hydroxyalkyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,         C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl,         C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,         C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl,         C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B),         C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl         moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5         substituents selected from the group consisting of CN, halogen,         C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,         (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or     -   two radicals R³ and R⁴ that are bound to the same carbon atom         form together with said carbon atom a saturated or partially         unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a         saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered         heterocycle, wherein the ring member atoms of the abovementioned         heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms         selected from the group of N, O and S, and wherein the         abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4         substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl,         C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of         the abovementioned cycles may be respectively replaced by one or         two C(═O) or C(═S) groups; -   n indicates the number of substituents R^(b) on the phenyl ring and     n is 0, 1, 2, 3 or 4; -   R^(b) is halogen, CN, NO₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl,     C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,     C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, NR^(A)R^(B), C(═NOR″)R′″ or     —C(═NH)—O—R′″,     -   it being possible for n=2, 3 or 4 that R^(b) are identical or         different; -   Het is a 5- or 6-membered heteroaryl, wherein the ring member atoms     of the heteroaryl include besides carbon atoms 1, 2, 3 or 4     heteroatoms selected from the group of N, O and S and wherein the     heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or     different groups R^(c):     -   R^(c) is halogen, CN, NO₂, NH₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl,         C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylamino,         di(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,         C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl,         C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl,         C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-haloalkoxy-C₁-C₄-alkyl,         C₂-C₆-alkenyl, C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″,         C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, phenyl, phenoxy,         phenoxy-C₁-C₄-alkyl or a 5- or 6-membered heteroaryl, wherein         the ring member atoms of the heteroaryl include besides carbon         atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O         and S, and wherein the aforementioned cyclic radicals are         unsubstituted or carry 1, 2, 3 or 4 identical or different         substituents R^(d):     -   R^(d) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or         C₁-C₄-haloalkoxy;     -   or two radicals R^(c) that are bound to adjacent ring member         atoms of the Het group form together with said ring member atoms         a fused 5-, 6- or 7-membered saturated, partially unsaturated or         aromatic carbocycle or heterocycle, wherein the ring member         atoms of the fused heterocycle include besides carbon atoms 1,         2, 3 or 4 heteroatoms selected from the group of N, O and S, and         wherein the fused carbocycle or heterocycle is unsubstituted or         carries 1, 2, 3 or 4 identical or different radicals groups         R^(e):     -   R^(e) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or         C₁-C₄-haloalkoxy;         and the N-oxides and the agriculturally acceptable salts of the         compounds of formula I.

The present invention furthermore relates to processes for preparing compounds of formula I. Accordingly a 4-halopyrimidine compound II, wherein Hal is halogen, preferably Cl or F, can be reacted with a suitable phenethyl amine compound III, wherein X is —CR³R⁴—, to obtain a compound I according to the present invention, wherein X is —CR³R⁴—, as shown in Scheme 1.

Generally, this reaction is carried out at temperatures of from 0 to 200° C., preferably from 50 to 170° C., in an inert organic solvent preferably in the presence of a base or a catalyst or a combination of a base and a catalyst (catalyst: e.g. NaF, KF, LiF, NaBr, KBr, LiBr, NaI, KI, LiI and ionic liquids, such as imidazolium catalysts).

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene; halogenated hydro-carbons such as chlorobenzene, dichlorobenzene; ethers such as dioxane, anisole and tetrahydrofuran (THF); nitriles such as acetonitrile and propionitrile; ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.-butyl methyl ketone; alcohols such as ethanol, n-propanol, isopropanol, n-butanol and tert.-butanol; and also dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP) and acetic acid ethyl ester, preferably DMSO, DMF, dimethyl acetamide, NMP, or NEP. Particular preference is given to NMP. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide; alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate; alkali metal amides such as lithium amide, sodium amide and potassium amide; alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium hydride and calcium hydride; alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, caesium carbonate; moreover organic bases, for example tertiary amines such as trimethyl-amine (TMA), triethylamine (TEA), tributylamine (TBA), diisopropylethylamine (DIPEA) and N-methyl-2-pyrrolidone (NMP), pyridine, substituted pyridines such as collidine, lutidine and 4 dimethylaminopyridine (DMAP), and also bicyclic amines. Preference is given to sodium hydride, potassium hydride, lithium carbonate, potassium carbonate, caesium carbonate, TEA, TBA and DIPEA, in particular DIPEA. The bases are generally employed in equimolar amounts, in excess or, if appropriate, as solvent. The amount of base is typically 1.1 to 5.0 molar equivalents relative to 1 mole of compounds II.

The starting materials are generally reacted with one another in equimolar amounts. In terms of yields, it may be advantageous to employ an excess of compounds III, based on 1.1 to 2.5 equivalents, preferred 1.1 to 1.5 equivalents of compounds II.

The compounds II are known from the literature or are commercially available or they can be prepared for example in analogy to methods described in: Heterocycles (2009) 78(7), 1627-1665; New J. Chem. (1994) 18(6), 701-8; WO 2005/095357; Science of Synthesis (2004) 16, 379-572; WO 2008/156726; WO 2006/072831; Organic Reactions (Hoboken, N.J., United States) (2000), 56; or Targets in Heterocyclic Systems (2008) 12, 59-84.

The phenethyl amine compounds III are known from the literature or are commercially available or they can be prepared for example in analogy to methods described in: WO 2007/046809; WO 2011/025505; or WO 2010/025451. Alternatively, compounds III in which R² is H and X is —CR³R⁴ can be prepared according to the general reaction in scheme 2:

Compound AD-1, in which the phenyl ring bears a hydroxyl group in ortho- or metha-position, is reacted with a heterocycle Het-LG, in which LG is a leaving group such as, e.g. F or Cl, in the presence of a base and/or a catalyst. Or compound AD-2, in which LG is a leaving group in para-position such as, e.g. F or Cl, is reacted with a hydroxyl-heterocycle HO-Het in the presence of a base and/or a catalyst according to procedures described in WO 2011032277 A1, WO 2008065393 A1, WO 2007096647 A2, WO 2007006714 A1, AU 2006201959 μl, DE 19518073 A1 (with catalyst: Organic Letters (2001), 3(26), 4315-4317; Journal of the American Chemical Society (1999), 121(18), 4369-4378) and provides Het-AD. Subsequent reaction with a nitroalkyl compound followed by a reduction leads to amine compounds III as described in Tetrahedron Letters (2003), 44(12), 2557-2560, Journal of Mass Spectrometry (2008), 43(4), 528-534, WO 2008039882 A1, Bioorganic & Medicinal Chemistry Letters (2007), 17(4), 974-977, Chemistry & Biodiversity (2005), 2(9), 1217-1231, Journal of Organic Chemistry (2005), 70(14), 5519-5527, Bioorganic & Medicinal Chemistry (2004), 12(15), 4055-4066 or Pesticide Science (1995), 44(4), 341-355.

Otherwise compounds III can be synthesized in analogy to WO 2011053835 A1, GB 2059955, WO 2007020227 A1, WO 2008046598 A1, WO 2011053835 A1, European Journal of Medicinal Chemistry (2009), 44(5), 2246-2251, Journal of Medicinal Chemistry (2007), 50(20), 5003-5011. Phenethylamines wherein R¹ and/or R² are not hydrogen are commercially available or can be prepared as outlined in scheme 3:

By addition of cyanide, a carbonyl compound AD-1 can be transformed into its cyano hyadrine (Chemistry A European Journal (2011), 17(44), 12276-12279; European Journal of Organic Chemistry (2002), (19), 3243-3249; Synlett (2003), (3), 353-356; Chirality (2009), 21(9), 836-842; Journal of Organic Chemistry (2008), 73(18), 7373-7375). Reduction of the nitrile group provides compounds AD-3 wherein R³ and R⁴ are hydrogen. Depending on the reaction conditions, the nitrile in AD-3 can be reduced and the hydroxyl group be removed in one step to furnish compounds III, wherein R³ and R⁴ are both hydrogen (Justus Liebigs Annalen der Chemie (1949), 564, 49-54, Justus Liebigs Annalen der Chemie (1957), 605, 200-11, Journal of the Chemical Society (1959), 1780-2, WO 2007020381 A2). Other conditions allow to preserve the hydroxyl group while selectively reducing the nitrile (Archiv der Pharmazie (Weinheim, Germany, 2011), 344(6), 372-385, Journal of the American Chemical Society (1948), 70, 3738-40, Journal of the American Chemical Society (1933), 55, 2593-7, Tetrahedron (2001), 57(40), 8573-8580, Chemical & Pharmaceutical Bulletin (2003), 51(6), 702-709;). This hydroxyl group can be transformed in a further step to provide halogen, cyano (Tetrahedron Letters (2007), 48(38), 6779-6784), amino, alkoxy groups by nucleophilic substitution in compounds such as III wherein R³ and R⁴ are hydrogen. It may be advantageous to couple AD-1 or AD-3 with a Het-LG prior to the abovementioned reactions as shown in scheme 2.

Phenethylamine compounds III, in which X is —CR³H— can also be prepared by reductive amination of ketone compounds AD-4 as described in scheme 4.

This conversion can be achieved using ammonia and a reducing agent or a metal organic compound or a cyanide source (Journal of the American Chemical Society (2011), 133(33), 12914-12917; Acta Pharmaceutica Suecica (1976), 13(1), 65-74; Journal of Medicinal Chemistry (1976), 19(6), 763-6; Journal of the American Chemical Society (1952), 74, 4611-15).

Phenethylamine compounds of the formula III, in which X is —CR³H—, can also be prepared by transformation of AD-1 to a nitro alkene AD-6 by first reacting it with nitro alkyl compounds AD-5 preferably in the presence of a base as described in scheme 5 (Journal of Organic Chemistry, 67(14), 4875-4881; 2002; European Journal of Medicinal Chemistry, 46(9), 3986-3995; 2011; Journal of the American Chemical Society, 107(12), 3601-6; 1985).

Consecutive reduction, e.g. with LiAlH₄ or hydrogen together with a suitable catalyst, leads to phenethylamine compounds III (Organic & Biomolecular Chemistry (2011), 9(23), 8171-8177, Journal of the American Chemical Society (2011), 133(31), 12197-12219, European Journal of Medicinal Chemistry (2010), 45(1), 11-18).

Alternatively, the nitro alkenes AD-6 can be reacted with an alkoxide to give the corresponding alkoxy compounds (European Journal of Medicinal Chemistry (2011), 46(9), 3986-3995, Organic Letters (2006), 8(20), 4481-4484, Tetrahedron (1999), 55(43), 12493-12514, Journal of Organic Chemistry (1995), 60(13), 4204-12)

Alternatively, the nitro alkenes can be reacted with metal cyanides to give the corresponding cyano compounds (Synlett (2008), (12), 1857-1861, Journal of Organic Chemistry (1985), 50(20), 3878-81). The terminal nitro group can be reduced selectively in the presence of the nitrile to yield compounds III, wherein R² is C₁-C₄-alkoxy or CN, respectively. It may be advantageous to couple AD-1 or AD-6 with a Het-LG prior to the abovementioned reactions as shown in scheme 2.

Alternatively, compounds of the formula III, in which X is —CH₂— can also be prepared by a process as described in scheme 6:

Substituted benzyl nitrile or phenyl acetaldehyde compounds AD-7 can be alkylated (Tetrahedron (1988), 44(15), 4737-46; US 20080171761 A1, Jingxi Huagong Zhongjianti (2010), 40(3), 26-28, Advanced Synthesis & Catalysis (2011), 353(2+3), 501-507) once or twice using alkylation agents which carry a suitable leaving group Y and can then be transformed to the corresponding amine by reduction of the nitrile or imine intermediate respectively (WO 2010081692 A1, Tetrahedron Letters (1985), 26(36), 4299-300; Journal of Organic Chemistry (1981), 46(4), 783-8; Tetrahedron (2002), 58(8), 1513-1518). It may be advantageous to couple AD-7 with a Het-LG prior to the abovementioned reactions as shown in scheme 2.

Furthermore, substituted benzyl nitriles AD-9, which are available from benzyl halides AD-8, can be used as intermediates for the preparation of phenethylamines III, wherein R³ and R⁴ are hydrogen, according to scheme 7 by way of reduction with an appropriate reducing agent (e.g. LiAlH₄, PhSiH₃ or H₂ and a catalyst: Tetrahedron (2011), 67(42), 8183-8186, WO 2011088181 A1, European Journal of Inorganic Chemistry (2011), 2011(22), 3381-3386, WO 2008124757 A1).

Further, compounds AD-9 can be used to obtain compounds III wherein at least one group R³ or R⁴ are not hydrogen. It is well known that benzyl nitriles such as AD-9 can undergo a selective addition of alkyl metals such as, for example, Grignard reagents R³MgHal, in which Hal stands for chlorine, bromine or iodine, either furnishing compounds III wherein R³ is not hydrogen and R⁴ is hydrogen by reduction of an intermediate imine AD-10 with an appropriate reducing agent such as NaBH₄, Bioorganic & Medicinal Chemistry Letters (2011), 21(5), 1434-1437, WO 2010136493 A1, WO 2008034142 A2, Synthesis (1986), (4), 301-3), or, in case an excess of alkyl metal is employed, to directly obtain compounds III, wherein R³ and R⁴ are identical and both are, for example, C₁-C₄-alkyl (Organic Process Research & Development (2011), 15(4), 871-875, Journal of Medicinal Chemistry (1999), 42(19), 3965-3970, WO 2009156100 A1).

Compounds III can also be synthesized by way of hydroboration of substituted alkenes AD-12 (scheme 8) followed by Suzuki coupling using palladium catalysis (Journal of Organic Chemistry (2007), 72(22), 8422-8426; Organic Letters (2007), 9(2), 203-206, Journal of the American Chemical Society (2005), 127(29), 10186-10187).

Compounds I in which X is —CH(C(═O)O—C₁-C₄-alkyl)-, —CH(C(═O)NH₂)—, —CH(C(═O)OH)— or —CHCN— can be prepared as follows or pursuing analogous procedures as in Scheme 9:

Tert-butyloxycarbonyl protected methyl ester AD-12 can be transformed to the corresponding biaryl ether AD-13 with suitable heteroaromatic groups Het-LG in analogy to WO 2005014534 A1, WO 2011100285 A1, Tetrahedron Letters (1994), 35(31), 5649-52. The coupling of AD-13 with 4-halopyrimidine compound II can be performed in analogy to Journal of Medicinal Chemistry (2011), 54(15), 5335-5348, Bioorganic & Medicinal Chemistry Letters (2011), 21(6), 1741-1743, US 20100068197 A1, WO 2005000246 A2, which leads to the formation of compounds I with Q being C₁-C₄-alkoxy (X is —CH(C(═O)—C₁-C₄-alkoxy)-). Saponificaton of the ester group with hydroxide bases leads to acid compounds I wherein X is —CH(C(═O)OH)—. Aminolysis of the ester group with ammonia and a catalyst (e.g. potassium cyanide) yields compounds I wherein X is —CH(C(═O)NH₂)—. Dehydratisation of the amide using POCl3 or trifluoro acetic acid anhydride with pyridine or treatment with other reagents capable to dehydrate a carboxamide such as, e.g., Burgess's reagent, leads to compound I, in which X is —CHCN— as described in WO 2006098961 A2.

A 4-halopyrimidine compound II, wherein Hal is halogen, preferably Cl or F, can be reacted with a suitable phenyl acetic acid amide compound III, wherein X is —C(═O)— to obtain a compound IVa

in analogy to scheme 1.

Generally, this reaction is carried out at temperatures of from 0 to 200° C., preferably from 50 to 170° C., in an inert organic solvent preferably in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.

Suitable catalysts are e.g. halides such as NaF, KF, LiF, NaBr, KBr, LiBr, NaI, KI, LiI; ionic liquids, such as imidazolium catalysts; transition metal catalysts like palladium, rhodium, ruthenium, iron, copper in the form of halides, pseudohalides, alkoxides, carboxylates (preferred acetate), complexes with dibenzylidene acetone and ligands like phosphine, phosphites, phosphoramidate ligands. Preferred ligands are bidentate and sterically demanding phosphorous ligands, even more preferably the catalysts are selected from 2,2′-bis(diphenyl-phosphanyl)-1,1′-binaphthyl, 2,2′-bis(diphenylphosphino)-1,1′-biphenyl, biphenyl-2-yldicyclohexylphosphine, 2-(dicyclohexylphosphino)-2′,6′-dimethoxy-1,1′-biphenyl, 1,1-bis(diphenylphosphino)ferrocene, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-propanediylbis[diphenylphosphine], 1,4-butanediylbis[diphenylphosphine] and 1,1′-(1,2-ethanediyl)bis[1-(2-methoxyphenyl)-1-phenyl-diposphine.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene; ethers such as dioxane, anisole and THF; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert.-butyl methyl ketone; alcohols such as ethanol, n-propanol, isopropanol, n-butanol and tert.-butanol; and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester. Preferably THF, DMSO, DMF, dimethyl acetamide, NMP or NEP are used; even more preferably THF, DMF or NMP are used. It is also possible to use mixtures of the solvents mentioned.

Suitable bases and their amounts are as described for the reaction with a phenethyl amine compound III, wherein X is —CR³R⁴—, as described above. The starting materials are generally reacted with one another in equimolar amounts. In terms of yields, it may be advantageous to employ an excess of compounds III, based on 1.1 to 2.5 equivalents, preferred 1.1 to 1.5 equivalents of compounds II.

The phenyl acetic acid amide compounds IIIa are known from the literature or are commercially available or they can be prepared for example in analogy to methods described in Organometallics (2011), 30(20), 5442-5451, WO 2010058030 A1 20100527, Journal of Organic Chemistry (1987), 52(21), 4689-93; GB 2016466 A.

Alternatively, amide compounds IVa can be synthesized by reacting 4-amino-pyrimidine compounds IIa [available by reaction of a chloropyrimidine II with excess of ammonia in analogy to methods described in WO 2011/147066, WO 2006/135719, US 2005/0245530 A1, J. Chem. Soc. (1951), 3439-44; Helv. Chim. Act. (1951), 34, 835-40] with the corresponding phenyl acetic acids IIIa in which Z is hydrogen or C₁-C₄-alkyl, which are commercially available, preferably in presence of AlMe₃ (1 to 3 equivalents) as stoichiometric reagent preferably in an inert organic solvent such as toluene (in analogy to US 2010/0063063 A1; WO 2005/011601; WO 2006/074884) as outlined in Scheme 10.

Compounds IVb can be prepared for example in analogy to methods described in US 20100022538 A1, J. Med. Chem. (2011), 54(9), 3241-3250, J. Org. Chem. (2011), 76(6), 1546-1553, Org. Lett. (2010), 12(23), 5570-5572.

Compounds I, wherein X is —C(═NR^(D))—, can be prepared from compounds IVa in analogy to Bioorg. Med. Chem. (2008) 16(8), 4600-4616, J. Med. Chem. (2004) 47(3), 663-672, Eur. J. Org. Chem. (2004) 5, 1025-1032, J. Med. Chem. (1987) 30(4), 720-1.

Compounds I, wherein X is —C(═NOR^(D))—, can be prepared from compounds IVa in analogy to WO 2007/075598 or from compounds IVb according to WO 2008/039520 and O'zbekiston Kimyo Jurnali (2004) 4, 3-6.

Compounds I and intermediates, wherein R is hydrogen, can be converted by conventional processes such as alkylation. Examples of suitable alkylating agents include alkyl halides, such as alkyl chloride, alkyl bromide or alkyl iodide, examples being methyl chloride, methyl bromide or methyl iodide, or dialkyl sulfates such as dimethyl sulfate or diethyl sulfate. The reaction with the alkylating agent is carried out advantageously in the presence of a solvent. Solvents used for these reactions are—depending on temperature range—aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene, chlorinated aliphatic and aromatic hydrocarbons such as DCM, chlorobenzene, open-chain dialkyl ethers such as diethyl ether, di-n-propyl ether, MTBE, cyclic ethers such as THF, 1,4-dioxane, glycol ethers such as dimethyl glycol ether, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, preferably DMF, DMSO, NMP or NEP, or mixtures of these solvents.

If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I. The N-oxides may be prepared from the compounds I according to conventional oxidation methods, e.g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. (1995), 38(11), 1892-1903,); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. (1981), 18 (7), 1305-1308) or oxone (cf. J. Am. Chem. Soc. (2001), 123 (25), 5962-5973). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g. under the action of light, acids or bases). Such conversions may also take place after use, e.g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatic purification of the crude products. In some cases, the intermediates and end products are obtained in the form of colorless or slightly viscous oils which can be freed from volatile components or purified under reduced pressure and at moderately elevated temperatures. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

The compounds of the present invention are useful for combating harmful fungi. Therefore the present invention furthermore relates to a method for combating harmful fungi, which process comprises treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula I or of an N-oxide or an agriculturally acceptable salt thereof.

Furthermore, the present invention also relates to seed comprising a compound of formula I, or an N-oxide or an agriculturally acceptable salt thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.

Agriculturally useful salts of the compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four C₁-C₄-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

Compounds I can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention. The compounds of formula I can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.

In respect of the variables, the embodiments of the intermediates correspond to the embodiments of the compounds of formula I. The term “compounds I” refers to compounds of formula I. Likewise, the term “compounds IIa” refers to compounds of formula IIa.

In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term “C_(n)-C_(m)” indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.

The term “halogen” refers to fluorine, chlorine, bromine and iodine.

The term “C₁-C₄-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, and 1,1-dimethylethyl. Likewise, the term “C₁-C₆-alkyl” refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms.

The term “C₁-C₄-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH₂—C₂F₅, CF₂—C₂F₅, CF(CF₃)₂, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise, the term “C₁-C₆-haloalkyl” refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms.

The term “C₁-C₄-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as defined above) which is bonded via an oxygen, at any position in the alkyl group, for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methyl

propoxy, 2-methylpropoxy or 1,1-dimethylethoxy. Likewise, the term “C₁-C₆-alkoxy” refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

The term “C₁-C₄-hydroxyalkyl” refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms (as defined above), wherein one hydrogen atom in these groups may be replaced by one hydroxy group, for example hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-propyl, 4-hydroxy-butyl.

The term “C₁-C₄-haloalkoxy” refers to a C₁-C₄-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH₂F, OCHF₂, OCF₃, OCH₂Cl, OCHCl₂, OCCl₃, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC₂F₅, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH₂—C₂F₅, OCF₂—C₂F₅, 1-(CH₂F)-2-fluoroethoxy, 1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromo

ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Likewise, the term “C₁-C₆-haloalkoxy” refers to a C₁-C₆-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above.

The term “C₁-C₄-alkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a C₁-C₄-alkoxy group (as defined above). Likewise, the term “C₁-C₆-alkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a C₁-C₆-alkoxy group (as defined above).

The term “C₁-C₄-haloalkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a C₁-C₄-haloalkoxy group (as defined above). Likewise, the term “C₁-C₆-haloalkoxy-C₁-C₄-alkyl” refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a C₁-C₆-alkoxy group (as defined above).

The term “C₁-C₄-alkylthio” as used herein refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as defined above) bonded via a sulfur atom, at any position in the alkyl group, for example methylthio, ethylthio, propylthio, isopropylthio, and n butylthio. Likewise, the term “C₁-C₆-alkylthio” as used herein refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the terms “C₁-C₄-haloalkylthio” and “C₁-C₆-haloalkylthio” as used herein refer to straight-chain or branched haloalkyl groups having 1 to 4 or 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the haloalkyl group.

The terms “C₁-C₄-alkylsulfinyl” or “C₁-C₆-alkylsulfinyl” refer to straight-chain or branched alkyl groups having 1 to 4 or 1 to 6 carbon atoms (as defined above) bonded through a —S(═O)— moiety, at any position in the alkyl group, for example methylsulfinyl and ethylsulfinyl, and the like. Accordingly, the terms “C₁-C₄-haloalkylsulfinyl” and “C₁-C₆-haloalkylsulfinyl”, respectively, refer to straight-chain or branched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)— moiety, at any position in the haloalkyl group.

The terms “C₁-C₄-alkylsulfonyl” and “C₁-C₆-alkylsulfonyl”, respectively, refer to straight-chain or branched alkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)₂— moiety, at any position in the alkyl group, for example methylsulfonyl. Accordingly, the terms “C₁-C₄-haloalkylsulfonyl” and “C₁-C₆-haloalkylsulfonyl”, respectively, refer to straight-chain or branched haloalkyl groups having 1 to 4 and 1 to 6 carbon atoms (as defined above), respectively, bonded through a —S(═O)₂— moiety, at any position in the haloalkyl group.

The term “C₁-C₄-alkylamino” refers to an amino radical carrying one C₁-C₄-alkyl group (as defined above) as substituent, for example methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-di-methylethylamino and the like. Likewise, the term “C₁-C₆-alkylamino” refers to an amino radical carrying one C₁-C₆-alkyl group (as defined above) as substituent.

The term “di(C₁-C₄-alkyl)amino” refers to an amino radical carrying two identical or different C₁-C₄-alkyl groups (as defined above) as substituents, for example dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N-methylamino, and the like. Likewise, the term “di(C₁-C₆-alkyl)amino” refers to an amino radical carrying two identical or different C₁-C₆-alkyl groups (as defined above) as substituents.

The term “(C₁-C₄-alkoxy)carbonyl” refers to a C₁-C₄-alkoxy radical (as defined above) which is attached via a carbonyl group.

The term “di(C₁-C₄-alkyl)aminocarbonyl” refers to a di(C₁-C₄)alkylamino radical as defined above which is attached via a carbonyl group.

The term “phenoxy” and refers to a phenyl radical which is attached via an oxygen atom. Likewise, the term “phenoxy-C₁-C₄-alkyl” and refers to a phenoxy radical which is attached via a C₁-C₄-alkyl group (as defined above).

The term “C₂-C₄-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl. Likewise, the term “C₂-C₆-alkenyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.

The term “C₂-C₄-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl. Likewise, the term “C₂-C₆-alkynyl” refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.

The term “C₃-C₈-cycloalkyl” refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl (C₃H₅), cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term “C₃-C₈-cycloalkyl-C₁-C₄-alkyl” refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via a C₁-C₄-alkyl group (as defined above).

The term “C₃-C₈-cycloalkyloxy” refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), which is bonded via an oxygen.

The term “saturated or partially unsaturated 3-, 4-5-, 6- or 7-membered carbocycle” is to be understood as meaning both saturated or partially unsaturated carbocycles having 3, 4, 5, 6 or 7 ring members. Examples include cyclopropyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl, and the like.

The term “saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S”, is to be understood as meaning both saturated and partially unsaturated heterocycles, for example:

-   -   a 3- or 4-membered saturated heterocycle which contains 1 or 2         heteroatoms from the group consisting of N, O and S as ring         members such as oxirane, aziridine, thiirane, oxetane,         azetidine, thiethane, [1,2]dioxetane, [1,2]dithietane,         [1,2]diazetidine; and     -   a 5- or 6-membered saturated or partially unsaturated         heterocycle which contains 1, 2 or 3 heteroatoms from the group         consisting of N, O and S as ring members such as         2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,         3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl,         3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,         3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,         3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl,         2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl,         4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl,         4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,         1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,         1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,         1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,         1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl,         2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl,         2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,         2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl,         2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,         2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,         2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,         2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,         2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,         2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,         2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,         2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,         2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,         2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,         3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,         3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,         4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,         4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl,         2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,         2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,         3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,         3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,         3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,         3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl,         2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl,         3-hexahydropyridazinyl, 4-hexahydropyridazinyl,         2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl,         5-hexahydropyrimidinyl, 2-piperazinyl,         1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl and         also the corresponding—ylidene radicals; and     -   a 7-membered saturated or partially unsaturated heterocycle such         as tetra- and hexahydroazepinyl, such as         2,3,4,5-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,         3,4,5,6-tetrahydro[2H]azepin-2-,-3-,-4-,-5-,-6- or -7-yl,         2,3,4,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,         2,3,6,7-tetrahydro[1H]azepin-1-,-2-,-3-,-4-,-5-,-6- or -7-yl,         hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and         hexahydrooxepinyl such as         2,3,4,5-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl,         2,3,4,7-tetrahydro[1H]oxepin-2-,-3-,-4-,-5-,-6- or -7-yl,         2,3,6,7-tetrahydro[1H]oxepin-2-, -3-,-4-,-5-,-6- or -7-yl,         hexahydroazepin-1-,-2-,-3- or -4-yl, tetra- and         hexahydro-1,3-diazepinyl, tetra- and hexahydro-1,4-diazepinyl,         tetra- and hexahydro-1,3-oxazepinyl, tetra- and         hexahydro-1,4-oxazepinyl, tetra- and hexahydro-1,3-dioxepinyl,         tetra- and hexahydro-1,4-dioxepinyl and the         corresponding—ylidene radicals; and

The term “5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S”, refers to, for example,

-   -   a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl,         pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl,         pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl,         imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl,         oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl,         isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl,         thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,         1,2,4-triazolyl-1-yl, 1,2,4-triazol-3-yl 1,2,4-triazol-5-yl,         1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and         1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl; or     -   a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl,         pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl,         pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and         1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.

The term “two radicals R^(c) that are bound to adjacent ring member atoms form together with said ring member atoms a fused cycle” refers to a condensed bicyclic ring system, wherein 5- or 6-membered heteroaryl carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring it being possible that these rings are saturated or partially saturated or aromatic.

The term “one or two CH₂ groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups” refers to an exchange of carbon atoms from a saturated or partially unsaturated 3-, 4-, 5-, 6- or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6- or 7-membered heterocycle, resulting in cycles such as cyclopropanone, cyclopentanone, cyclopropanethione, cyclopentanethione, 5-oxazolone, cyclohexane-1,4-dione, cyclohexane-1,4-dithione, cyclohex-2-ene-1,4-dione or cyclohex-2-ene-1,4-dithione.

As regards the fungicidal activity of the compounds I, I.A, I.B or I.C preference is given to those compounds, wherein the substituents and variables (e.g. R^(a2), R^(a5), R^(a6), R, X, R¹, R², R³, R⁴, R^(b), R^(c), R′, R′″, R^(A), R^(B), R^(D), Het, n) have independently of each other or more preferably in combination the following meanings:

A further embodiment relates to compounds I wherein R^(a2) and R^(a5) independently of each other are preferably selected from the group consisting of hydrogen, halogen, CN, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyloxy, (C₁-C₄-alkoxy)carbonyl. Further preferred embodiments relate to compounds I wherein R^(a2) and R^(a5) independently of each other are hydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy and (C₁-C₄-alkoxy)carbonyl. Further preferred embodiments relate to compounds I wherein R^(a2) and R^(a5) independently of each other are halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalk-oxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy or (C₁-C₄-alkoxy)carbonyl, and it being possible that one of both, R^(a2) or R^(a5) can in addition be hydrogen. Further preferred embodiments relate to compounds I wherein R^(a2) and R^(a5) independently of each other are hydrogen, Cl, F, CH₃, CH₂CH₃, OCH₃, OCF₃, CH₂OCH₃, CN, OCH₂OCH, CF₃, CHFCH₃, COOCH₃ or COOCH₂CH₃.

Further preferred embodiments relate to compounds I wherein R^(a5) is Cl.

Further preferred embodiments relate to compounds I wherein R^(a5) is F.

Further preferred embodiments relate to compounds I wherein R^(a5) is CH₃.

Further preferred embodiments relate to compounds I wherein R^(a5) is OCH₃.

In the compounds I according to the invention, R^(A), R^(B) in radicals R^(a2) and R^(a5) independently of one another preferably are hydrogen, C₁-C₄-alkyl.

In the compounds I according to the invention, R′ in radicals R^(a2) and R^(a5) preferably is hydrogen, NH₂, C₁-C₄-alkyl, C₁-C₄-alkoxy. In the compounds I according to the invention, R″ in radicals R^(a2) and R^(a5) preferably is hydrogen, C₁-C₄-alkyl. In the compounds I according to the invention, R″ in radicals R^(a2) and R^(a5) preferably is hydrogen.

Further preferred embodiments relate to compounds I wherein R^(a2) and R^(a5) in each case are one of the following combinations in line 1 to line 196 in table A:

TABLE A line R^(a2) R^(a5) 1 H H 2 CH₃ H 3 CH₂CH₃ H 4 OCH₃ H 5 CH₂OCH₃ H 6 OCH₂OCH₃ H 7 CF₃ H 8 CHFCH₃ H 9 CN H 10 F H 11 Cl H 12 COOCH₃ H 13 COOCH₂CH₃ H 14 OCF₃ H 15 H CH₃ 16 CH₃ CH₃ 17 CH₂CH₃ CH₃ 18 OCH₃ CH₃ 19 CH₂OCH₃ CH₃ 20 OCH₂OCH₃ CH₃ 21 CF₃ CH₃ 22 CHFCH₃ CH₃ 23 CN CH₃ 24 F CH₃ 25 Cl CH₃ 26 COOCH₃ CH₃ 27 COOCH₂CH₃ CH₃ 28 OCF₃ CH₃ 29 H CH₂CH₃ 30 CH₃ CH₂CH₃ 31 CH₂CH₃ CH₂CH₃ 32 OCH₃ CH₂CH₃ 33 CH₂OCH₃ CH₂CH₃ 34 OCH₂OCH₃ CH₂CH₃ 35 CF₃ CH₂CH₃ 36 CHFCH₃ CH₂CH₃ 37 CN CH₂CH₃ 38 F CH₂CH₃ 39 Cl CH₂CH₃ 40 COOCH₃ CH₂CH₃ 41 COOCH₂CH₃ CH₂CH₃ 42 OCF₃ CH₂CH₃ 43 H OCH₃ 44 CH₃ OCH₃ 45 CH₂CH₃ OCH₃ 46 OCH₃ OCH₃ 47 CH₂OCH₃ OCH₃ 48 OCH₂OCH₃ OCH₃ 49 CF₃ OCH₃ 50 CHFCH₃ OCH₃ 51 CN OCH₃ 52 F OCH₃ 53 Cl OCH₃ 54 COOCH₃ OCH₃ 55 COOCH₂CH₃ OCH₃ 56 OCF₃ OCH₃ 57 H CH₂OCH₃ 58 CH₃ CH₂OCH₃ 59 CH₂CH₃ CH₂OCH₃ 60 OCH₃ CH₂OCH₃ 61 CH₂OCH₃ CH₂OCH₃ 62 OCH₂OCH₃ CH₂OCH₃ 63 CF₃ CH₂OCH₃ 64 CHFCH₃ CH₂OCH₃ 65 CN CH₂OCH₃ 66 F CH₂OCH₃ 67 Cl CH₂OCH₃ 68 COOCH₃ CH₂OCH₃ 69 COOCH₂CH₃ CH₂OCH₃ 70 OCF₃ CH₂OCH₃ 71 H OCH₂OCH₃ 72 CH₃ OCH₂OCH₃ 73 CH₂CH₃ OCH₂OCH₃ 74 OCH₃ OCH₂OCH₃ 75 CH₂OCH₃ OCH₂OCH₃ 76 OCH₂OCH₃ OCH₂OCH₃ 77 CF₃ OCH₂OCH₃ 78 CHFCH₃ OCH₂OCH₃ 79 CN OCH₂OCH₃ 80 F OCH₂OCH₃ 81 Cl OCH₂OCH₃ 82 COOCH₃ OCH₂OCH₃ 83 COOCH₂CH₃ OCH₂OCH₃ 84 OCF₃ OCH₂OCH₃ 85 H CF₃ 86 CH₃ CF₃ 87 CH₂CH₃ CF₃ 88 OCH₃ CF₃ 89 CH₂OCH₃ CF₃ 90 OCH₂OCH₃ CF₃ 91 CF₃ CF₃ 92 CHFCH₃ CF₃ 93 CN CF₃ 94 F CF₃ 95 Cl CF₃ 96 COOCH₃ CF₃ 97 COOCH₂CH₃ CF₃ 98 OCF₃ CF₃ 99 H CHFCH₃ 100 CH₃ CHFCH₃ 101 CH₂CH₃ CHFCH₃ 102 OCH₃ CHFCH₃ 103 CH₂OCH₃ CHFCH₃ 104 OCH₂OCH₃ CHFCH₃ 105 CF₃ CHFCH₃ 106 CHFCH₃ CHFCH₃ 107 CN CHFCH₃ 108 F CHFCH₃ 109 Cl CHFCH₃ 110 COOCH₃ CHFCH₃ 111 COOCH₂CH₃ CHFCH₃ 112 OCF₃ CHFCH₃ 113 H CN 114 CH₃ CN 115 CH₂CH₃ CN 116 OCH₃ CN 117 CH₂OCH₃ CN 118 OCH₂OCH₃ CN 119 CF₃ CN 120 CHFCH₃ CN 121 CN CN 122 F CN 123 Cl CN 124 COOCH₃ CN 125 COOCH₂CH₃ CN 126 OCF₃ CN 127 H F 128 CH₃ F 129 CH₂CH₃ F 130 OCH₃ F 131 CH₂OCH₃ F 132 OCH₂OCH₃ F 133 CF₃ F 134 CHFCH₃ F 135 CN F 136 F F 137 Cl F 138 COOCH₃ F 139 COOCH₂CH₃ F 140 OCF₃ F 141 H Cl 142 CH₃ Cl 143 CH₂CH₃ Cl 144 OCH₃ Cl 145 CH₂OCH₃ Cl 146 OCH₂OCH₃ Cl 147 CF₃ Cl 148 CHFCH₃ Cl 149 CN Cl 150 F Cl 151 Cl Cl 152 COOCH₃ Cl 153 COOCH₂CH₃ Cl 154 OCF₃ Cl 155 H COOCH₃ 156 CH₃ COOCH₃ 157 CH₂CH₃ COOCH₃ 158 OCH₃ COOCH₃ 159 CH₂OCH₃ COOCH₃ 160 OCH₂OCH₃ COOCH₃ 161 CF₃ COOCH₃ 162 CHFCH₃ COOCH₃ 163 CN COOCH₃ 164 F COOCH₃ 165 Cl COOCH₃ 166 COOCH₃ COOCH₃ 167 COOCH₂CH₃ COOCH₃ 168 OCF₃ COOCH₃ 169 H COOCH₂CH₃ 170 CH₃ COOCH₂CH₃ 171 CH₂CH₃ COOCH₂CH₃ 172 OCH₃ COOCH₂CH₃ 173 CH₂OCH₃ COOCH₂CH₃ 174 OCH₂OCH₃ COOCH₂CH₃ 175 CF₃ COOCH₂CH₃ 176 CHFCH₃ COOCH₂CH₃ 177 CN COOCH₂CH₃ 178 F COOCH₂CH₃ 179 Cl COOCH₂CH₃ 180 COOCH₃ COOCH₂CH₃ 181 COOCH₂CH₃ COOCH₂CH₃ 182 OCF₃ COOCH₂CH₃ 183 H OCF₃ 184 CH₃ OCF₃ 185 CH₂CH₃ OCF₃ 186 OCH₃ OCF₃ 187 CH₂OCH₃ OCF₃ 188 OCH₂OCH₃ OCF₃ 189 CF₃ OCF₃ 190 CHFCH₃ OCF₃ 191 CN OCF₃ 192 F OCF₃ 193 Cl OCF₃ 194 COOCH₃ OCF₃ 195 COOCH₂CH₃ OCF₃ 196 OCF₃ OCF₃

In the compounds I according to the invention, R^(a6) preferably is chlorine.

In the compounds I according to the invention, R^(a6) preferably is fluorine.

In the compounds I according to the invention, R^(a6) preferably is bromine.

In the compounds I according to the invention, R is preferably selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, CN, CH₂CN or CH₂—O—C(═O)R′, wherein R′ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy; more preferably R is selected from the group consisting of hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl and C₂-C₄-alkynyl; most preferably R is hydrogen or C₁-C₄-alkyl.

Another particularly preferred embodiment relates to compounds I wherein R is hydrogen; yet another preferred embodiment relates to compounds I wherein R is CH₃. Further preferred embodiments relate to compounds I wherein R is in each case one of the following groups I-1 to I-2 in table I:

TABLE I No. R I-1 H I-2 CH₃

In the compounds I according to the invention, X is preferably —CH₂—, —CH(CH₃)—, —CH(CH₂CH₃)—, —C(CH₃)₂—, —CHCN—, —CH(C(═O)—C₁-C₄-alkoxy)-, —CH(C(═O)NH₂)—, —C(═O)N(C₁-C₄-alkyl)₂- and —CH(C(═O)OH)—; more preferably X is —CH₂— or —CH(CH₂OH)—, in particular X is —CH₂—. Further preferred embodiments relate to compounds I wherein X is in each case one of the following groups II-1 to II-7 in table II:

TABLE II No. X II-1 —CH₂— II-2 —C(═O)— II-3 —CH(CH₃)— II-4 —C(CH₃)₂— II-5 —CH(C₂H₅)— II-6 —CHCN— II-7 —CH(CH₂OH)—

In the compounds I according to the invention, R¹ and R² independently of each other are preferably selected from the group consisting of hydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₃-C₈-cycloalkyl; more preferably R¹ and R² independently of each other are hydrogen, CN, CH₃, CH₂CH₃, F, Cl or OCH₃; another more preferred embodiment relates to compounds I wherein R¹ and R² independently of each other are hydrogen or CH₃; more preferably R¹ and R² are hydrogen.

Further preferred embodiments relate to compounds I wherein R¹ and R² in each case are one of the following combinations III-1 to III-7 in table III:

TABLE III No. R¹ R² III-1 H H III-2 CH₃ H III-3 CN H III-4 F H III-5 Cl H III-6 OCH₃ H III-7 CH₃ CH₃

In the compounds I according to the invention, R^(b) is preferably selected from the group consisting of halogen, CN, NO₂, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkoxy-C₁-C₄-alkyl; more preferably R^(b) is selected from the group consisting of halogen, CN, C₁-C₄-haloalkyl and C₁-C₄-alkoxy; most preferably R^(b) is halogen, CN, CH₃, CF₃, OCH₃.

In the compounds I according to the invention, n is preferably 0.

A further embodiment relates to compounds I wherein n is preferably 1.

A further embodiment relates to compounds I wherein n is preferably 2.

A further embodiment relates to compounds I wherein n is preferably 3.

A further embodiment relates to compounds I wherein n is preferably 4.

In the compounds I according to the invention, Het is preferably selected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; more preferably Het is selected from pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl; preferably Het is pyrimidin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiazol-2-yl; more preferably Het is unsubstituted; a further preferred embodiment relates to compounds I wherein Het is substituted by 1 radical R^(c); another preferred embodiment relates to compounds I wherein Het is substituted by 2 radicals R^(c); yet another preferred embodiment relates to compounds I wherein Het is substituted by 3 radicals R^(c); another preferred embodiment relates to compounds I wherein Het is substituted by 4 radicals R.

Preferred embodiments of the invention relate to compounds I, in which the group Het is one of the following radicals H-1 to H-38 in table H:

TABLE H No. Het H-1 

H-2 

H-3 

H-4 

H-5 

H-6 

H-7 

H-8 

H-9 

H-10

H-11

H-12

H-13

H-14

H-15

H-16

H-17

H-18

H-19

H-20

H-21

H-22

H-23

H-24

H-25

H-26

H-27

H-28

H-29

H-30

H-31

H-32

H-33

H-34

H-35

H-36

H-37

H-38

in which # indicates the point of attachment.

In the compounds I according to the invention, R^(c) is preferably selected from the group consisting of halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″, C₃-C₈-cycloalkyl, phenyl and phenoxy. A further embodiment relates to compounds I wherein R^(c) is F, Cl, CN, CH₃, OCH₃, CF₃, OCF₃ or COOCH₃; most preferably R^(c) is Cl, CN, CF₃.

With respect to their use, particular preference is given to the compounds I.A:

With respect to their use, particular preference is also given to the compounds I.B:

With respect to their use, particular preference is also given to the compounds I.C:

According to a further embodiment, the present invention relates to compounds of the formula I.A wherein:

-   R^(a2), R^(a5) independently of each other are hydrogen, halogen,     CN, NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,     C₁-C₄-haloalkoxy or (C₁-C₄-alkoxy)carbonyl; -   R^(a6) is halogen; -   R is hydrogen or C₁-C₄-alkyl; -   X is a divalent group —CR³R⁴—; wherein     -   R³, R⁴ independently of each other are hydrogen, C₁-C₄-alkyl,         C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl or         (C₁-C₄-alkoxy)carbonyl; -   R¹, R² independently of each other are hydrogen or C₁-C₄-alkyl; -   n indicates the number of substituents R^(b) on the phenyl ring and     n is 0 or 1; -   R^(b) is halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy; -   Het is a pyridinyl or pyrimidinyl wherein the pyridinyl or     pyrimidinyl is unsubstituted or carries 1 or 2 groups R^(c):     -   R^(c) is halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy         or C₁-C₆-haloalkoxy; and         the N-oxides and the agriculturally acceptable salts of the         compounds of formula I.A.

The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e.g. wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

The term “plant propagation material” is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.

These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agri_products.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. candida) and sunflowers (e.g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e.g. spot blotch (B. sorokiniana) on cereals and e.g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph: B. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C. lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides); Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi), such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ‘rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e.g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphani-dermatum); Ramularia spp., e.g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e.g. S. sclerotiorum) and soybeans (e.g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana: head smut), sorghum and sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e.g. U. betae); Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. dahliae on strawberries, rape, potatoes and tomatoes.

The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term “protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, coiling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.

The compounds I and compositions thereof, resepectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.

The term “plant health” is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves (“greening effect”)), quality (e.g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

The compounds of the formula (I) can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.

The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.

The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.

An agrochemical composition comprises a fungicidally effective amount of a compound I. The term “effective amount” denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.

The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; dimethyl sulfoxide (DMSO); ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.

Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides.

Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.

Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.

Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.

The following list of active substances, in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:

A) Respiration inhibitors

-   -   Inhibitors of complex III at Qo site (e.g. strobilurins):         azoxystrobin, coumethoxy-strobin, coumoxystrobin, dimoxystrobin,         enestroburin, fenaminstrobin, fenoxy-strobin/flufenoxystrobin,         fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,         picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,         trifloxystrobin,         2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid         methyl ester and         2-(2-(3-(2,6-di-chlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide,         pyribencarb, triclopyricarb/chlorodincarb, famoxadone,         fenamidone;     -   inhibitors of complex III at Qi site: cyazofamid, amisulbrom,         [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,         [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,         [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate,         [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate;     -   inhibitors of complex II (e.g. carboxamides): benodanil,         bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil,         fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin,         penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide,         N-(4′-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,         N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide,         N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide;     -   other respiration inhibitors (e.g. complex I, uncouplers):         diflumetorim,         (5,8-difluoro-quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine;         nitrophenyl derivates: binapacryl, dinobuton, dinocap,         fluazinam; ferimzone; organometal compounds: fentin salts, such         as fentin-acetate, fentin chloride or fentin hydroxide;         ametoctradin; and silthiofam;         B) Sterol biosynthesis inhibitors (SBI fungicides)     -   C14 demethylase inhibitors (DMI fungicides): triazoles:         azaconazole, bitertanol, bromuconazole, cyproconazole,         difenoconazole, diniconazole, diniconazole-M, epoxiconazole,         fenbuconazole, fluquinconazole, flusilazole, flutriafol,         hexaconazole, imibenconazole, ipconazole, metconazole,         myclobutanil, oxpoconazole, paclobutrazole, penconazole,         propiconazole, prothioconazole, simeconazole, tebuconazole,         tetraconazole, triadimefon, triadimenol, triticonazole,         uniconazole; imidazoles: imazalil, pefurazoate, prochloraz,         triflumizol; pyrimidines, pyridines and piperazines: fenarimol,         nuarimol, pyrifenox, triforine;     -   Delta14-reductase inhibitors: aldimorph, dodemorph,         dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin,         piperalin, spiroxamine;     -   Inhibitors of 3-keto reductase: fenhexamid;         C) Nucleic acid synthesis inhibitors     -   phenylamides or acyl amino acid fungicides: benalaxyl,         benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam),         ofurace, oxadixyl;     -   others: hymexazole, octhilinone, oxolinic acid, bupirimate,         5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine,         5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;         D) Inhibitors of cell division and cytoskeleton     -   tubulin inhibitors, such as benzimidazoles, thiophanates:         benomyl, carbendazim, fuberidazole, thiabendazole,         thiophanate-methyl; triazolopyrimidines:         5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine     -   other cell division inhibitors: diethofencarb, ethaboxam,         pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;         E) Inhibitors of amino acid and protein synthesis     -   methionine synthesis inhibitors (anilino-pyrimidines):         cyprodinil, mepanipyrim, pyrimethanil;     -   protein synthesis inhibitors: blasticidin-S, kasugamycin,         kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin,         oxytetracyclin, polyoxine, validamycin A;         F) Signal transduction inhibitors     -   MAP/histidine kinase inhibitors: fluoroimid, iprodione,         procymidone, vinclozolin, fenpiclonil, fludioxonil;     -   G protein inhibitors: quinoxyfen;         G) Lipid and membrane synthesis inhibitors     -   Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos,         pyrazophos, isoprothiolane;     -   lipid peroxidation: dicloran, quintozene, tecnazene,         tolclofos-methyl, biphenyl, chloroneb, etridiazole;     -   phospholipid biosynthesis and cell wall deposition:         dimethomorph, flumorph, mandipropamid, pyrimorph,         benthiavalicarb, iprovalicarb, valifenalate and         N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic         acid-(4-fluorophenyl) ester;     -   compounds affecting cell membrane permeability and fatty acides:         propamocarb, propamocarb-hydrochlorid         H) Inhibitors with Multi Site Action     -   inorganic active substances: Bordeaux mixture, copper acetate,         copper hydroxide, copper oxychloride, basic copper sulfate,         sulfur;     -   thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,         metiram, propineb, thiram, zineb, ziram;     -   organochlorine compounds (e.g. phthalimides, sulfamides,         chloronitriles): anilazine, chlorothalonil, captafol, captan,         folpet, dichlofluanid, dichlorophen, flusulfamide,         hexachlorobenzene, pentachlorphenole and its salts, phthalide,         tolylfluanid,         N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;     -   guanidines and others: guanidine, dodine, dodine free base,         guazatine, guazatine-acetate, iminoctadine,         iminoctadine-triacetate, iminoctadine-tris(albesilate),         dithianon;         I) Cell wall synthesis inhibitors     -   inhibitors of glucan synthesis: validamycin, polyoxin B; melanin         synthesis inhibitors:     -   pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;         J) Plant defence inducers     -   acibenzolar-5-methyl, probenazole, isotianil, tiadinil,         prohexadione-calcium;     -   phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and         its salts;         K) Unknown mode of action     -   bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet,         debacarb, diclo-mezine, difenzoquat, difenzoquat-methylsulfate,         diphenylamin, fenpyrazamine, flumetover, flusulfamide,         flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl,         oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide,         2-butoxy-6-iodo-3-propylchromen-4-one,         N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl         acetamide,         N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl         formamidine,         N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl         formamidine,         N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl         formamidine,         N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl         formamidine,         2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-carboxylic         acid methyl-(1,2,3,4-tetrahydro-naphthalen-1-yl)-amide,         2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]piperidin-4-yl}-thiazole-4-carboxylic         acid methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-amide,     -   1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,         methoxy-acetic acid         6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester,         N-Methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide,         3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]pyridine,         3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine         (pyrisoxazole), N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic         acid amide,         5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole,     -   2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;         L) Antifungal biocontrol agents, plant bioactivators:         Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH &         Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from         Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from         bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession         No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc.,         USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in         RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc.,         USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g.         TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila         1-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana         (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from         Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g.         ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f.         catenulata, also named Gliocladium catenulatum (e.g. isolate         J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans         (e.g. CONTANS® from Prophyta, Germany), Cryphonectria parasitica         (e.g. Endothia parasitica from CNICM, France), Cryptococcus         albidus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South         Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A.,         Italy, FUSACLEAN® from Natural Plant Protection, France),         Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel),         Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France),         Phlebiopsis gigantea (e.g. ROTSOP® from Verdera, Finland),         Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co.         Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from         Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis         (e.g. REGALIA® from Marrone BioInnovations, USA), Talaromyces         flavus V117b (e.g. PROTUS® from Prophyta, Germany), Trichoderma         asperellum SKT-1 (e.g. ECO—HOPE® from Kumiai Chemical Industry         Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from         Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g.         PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35         (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39         (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd.,         Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride         (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum         ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro         Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB®         from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g.         TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g.         SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from         Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T.         Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1         from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g.         BOTRY-ZEN® from Botry-Zen Ltd, NZ);         M) Growth regulators     -   abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,         brassinolide, butralin, chlormequat (chlormequat chloride),         choline chloride, cyclanilide, daminozide, dikegulac,         dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin,         flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid,         inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide,         mepiquat (mepiquat chloride), naphthaleneacetic acid,         N-6-benzyladenine, paclobutrazol, prohexadione         (prohexadione-calcium), prohydrojasmon, thidiazuron,         triapenthenol, tributyl phosphorotrithioate,         2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;         N) Herbicides     -   acetamides: acetochlor, alachlor, butachlor, dimethachlor,         dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor,         napropamide, naproanilide, pethoxamid, pretilachlor, propachlor,         thenylchlor;         -   amino acid derivatives: bilanafos, glyphosate, glufosinate,             sulfosate;         -   aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl,             fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop,             quizalofop, quizalofop-P-tefuryl;         -   Bipyridyls: diquat, paraquat;         -   (thio)carbamates: asulam, butylate, carbetamide,             desmedipham, dimepiperate, eptam (EPTC), esprocarb,             molinate, orbencarb, phenmedipham, prosulfocarb,             pyributicarb, thiobencarb, triallate;         -   cyclohexanediones: butroxydim, clethodim, cycloxydim,             profoxydim, sethoxydim, tepraloxydim, tralkoxydim;         -   dinitroanilines: benfluralin, ethalfluralin, oryzalin,             pendimethalin, prodiamine, trifluralin;         -   diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop,             ethoxyfen, fomesafen, lactofen, oxyfluorfen;         -   hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;         -   imidazolinones: imazamethabenz, imazamox, imazapic,             imazapyr, imazaquin, imazethapyr;         -   phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic             acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl,             MCPB, Mecoprop;         -   pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet,             norflurazon, pyridate;         -   pyridines: aminopyralid, clopyralid, diflufenican,             dithiopyr, fluridone, fluoroxypyr, picloram, picolinafen,             thiazopyr;         -   sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron,             chlorimuron-ethyl, chlorsulfuron, cinosulfuron,             cyclosulfamuron, ethoxysulfuron, flazasulfuron,             flucetosulfuron, flupyrsulfuron, foramsulfuron,             halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron,             metazosulfuron, metsulfuron-methyl, nicosulfuron,             oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron,             rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron,             triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron,             tritosulfuron,             1-((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yOsulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;         -   triazines: ametryn, atrazine, cyanazine, dimethametryn,             ethiozin, hexazinone, metamitron, metribuzin, prometryn,             simazine, terbuthylazine, terbutryn, triaziflam;         -   ureas: chlorotoluron, daimuron, diuron, fluometuron,             isoproturon, linuron, metha-benzthiazuron, tebuthiuron;         -   other acetolactate synthase inhibitors: bispyribac-sodium,             cloransulam-methyl, diclosulam, florasulam, flucarbazone,             flumetsulam, metosulam, ortho-sulfamuron, penoxsulam,             propoxycarbazone, pyribambenz-propyl, pyribenzoxim,             pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,             pyroxasulfone, pyroxsulam;         -   others: amicarbazone, aminotriazole, anilofos, beflubutamid,             benazolin, bencarbazone, benfluresate, benzofenap,             bentazone, benzobicyclon, bicyclopyrone, bromacil,             bromobutide, butafenacil, butamifos, cafenstrole,             carfentrazone, cinidon-ethyl, chlorthal, cinmethylin,             clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat,             diflufenzopyr, Drechslera monoceras, endothal, ethofumesate,             etobenzanid, fenoxasulfone, fentrazamide,             flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridone,             flurtamone, indanofan, isoxaben, isoxaflutole, lenacil,             propanil, propyzamide, quinclorac, quinmerac, mesotrione,             methyl arsonic acid, naptalam, oxadiargyl, oxadiazon,             oxaziclomefone, pentoxazone, pinoxaden, pyraclonil,             pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate,             quinoclamine, saflufenacil, sulcotrione, sulfentrazone,             terbacil, tefuryltrione, tembotrione, thiencarbazone,             topramezone,             (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic             acid ethyl ester,             6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid             methyl ester,             6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,             4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic             acid,             4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic             acid methyl ester, and             4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carboxylic             acid methyl ester.             O) Insecticides     -   organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,         chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,         dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,         fenitrothion, fenthion, isoxathion, malathion, methamidophos,         methidathion, methyl-parathion, mevinphos, monocrotophos,         oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,         phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,         profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,         triazophos, trichlorfon;     -   carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb,         carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,         methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb,         triazamate;     -   pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,         cyphenothrin, cypermethrin, alpha-cypermethrin,         beta-cypermethrin, zeta-cypermethrin, deltamethrin,         esfenvalerate, etofenprox, fenpropathrin, fenvalerate,         imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,         pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate,         tefluthrin, tetramethrin, tralomethrin, transfluthrin,         profluthrin, dimefluthrin;     -   insect growth regulators: a) chitin synthesis inhibitors:         benzoylureas: chlorfluazuron, cyramazin, diflubenzuron,         flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,         teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,         etoxazole, clofentazine; b) ecdysone antagonists: halofenozide,         methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:         pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis         inhibitors: spirodiclofen, spiromesifen, spirotetramat;     -   nicotinic receptor agonists/antagonists compounds: clothianidin,         dinotefuran, imidacloprid, thiamethoxam, nitenpyram,         acetamiprid, thiacloprid,         1-(2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;     -   GABA antagonist compounds: endosulfan, ethiprole, fipronil,         vaniliprole, pyrafluprole, pyriprole,         5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H-pyrazole-3-carbothioic         acid amide;     -   macrocyclic lactone insecticides: abamectin, emamectin,         milbemectin, lepimectin, spinosad, spinetoram;     -   mitochondrial electron transport inhibitor (METI) I acaricides:         fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;     -   METI II and III compounds: acequinocyl, fluacyprim,         hydramethylnon;     -   Uncouplers: chlorfenapyr;     -   oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron,         fenbutatin oxide, propargite;     -   moulting disruptor compounds: cryomazine;     -   mixed function oxidase inhibitors: piperonyl butoxide;     -   sodium channel blockers: indoxacarb, metaflumizone;     -   others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,         pymetrozine, sulfur, thiocyclam, flubendiamide,         chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen,         flupyrazofos, cyflumetofen, amidoflumet, imicyafos,         bistrifluoron, pyrifluquinazon and         1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1′-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]cyclopropaneacetic         acid ester.

The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one further active substance useful for plant protection, e.g. selected from the groups A) to O) (component 2), in particular one further fungicide, e.g. one or more fungicide from the groups A) to L), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to L), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to L). By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).

This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e.g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.

In binary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and one further active substance (component 2), e.g. one active substance from groups A) to O), the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:3 to 3:1. In ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1) and a first further active substance (component 2) and a second further active substance (component 3), e.g. two active substances from groups A) to O), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1, and the weight ratio of component 1 and component 3 preferably is in the range of from 1:50 to 50:1 and particularly in the range of from 1:10 to 10:1.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group A) (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin; famoxadone, fenamidone; bixafen, boscalid, fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such as fentin acetate.

Preference is given to mixtures comprising a compound I (component 1) and at least one active substance selected from group B) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, fenarimol, triforine; dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine; fenhexamid.

Preference is given to mixtures comprising a compound I (component 1) and at least one active substance selected from group C) (component 2) and particularly selected from metalaxyl, (metalaxyl-M) mefenoxam, ofurace.

Preference is given to mixtures comprising a compound I (component 1) and at least one active substance selected from group D) (component 2) and particularly selected from benomyl, carbendazim, thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone, pyriofenone.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group E) (component 2) and particularly selected from cyprodinil, mepanipyrim, pyrimethanil.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group F) (component 2) and particularly selected from iprodione, fludioxonil, vinclozolin, quinoxyfen.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group G) (component 2) and particularly selected from dimethomorph, flumorph, iprovalicarb, benthiavalicarb, mandipropamid, propamocarb.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group H) (component 2) and particularly selected from copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb, thiram, captafol, folpet, chlorothalonil, dichlofluanid, dithianon.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group I) (component 2) and particularly selected from carpropamid and fenoxanil.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group J) (component 2) and particularly selected from acibenzolar-5-methyl, probenazole, tiadinil, fosetyl, fosetyl-aluminium, H₃PO₃ and salts thereof.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group K) (component 2) and particularly selected from cymoxanil, proquinazid and N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide.

Preference is also given to mixtures comprising a compound I (component 1) and at least one active substance selected from group L) (component 2) and particularly selected from Bacillus subtilis strain NRRL No. B-21661, Bacillus pumilus strain NRRL No. B-30087 and Ulocladium oudemansii.

Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1) and one further active substance (component 2), which further active substance is selected from the column “Component 2” of the lines D-1 to D-370 of Table D.

A further embodiment relates to the compositions D-1 to D-370 listed in Table D, where a row of Table D corresponds in each case to a fungicidal composition comprising one of the in the present specification individualized compounds of formula I (component 1) and the respective further active substance from groups A) to O) (component 2) stated in the row in question.

Preferably, the compositions described comprise the active substances in synergistically effective amounts.

TABLE D Composition comprising one indiviualized compound I and one further active substance from groups A) to O) Mixture Component 1 Component 2 D-1 one individualized compound I Azoxystrobin D-2 one individualized compound I Coumethoxystrobin D-3 one individualized compound I Coumoxystrobin D-4 one individualized compound I Dimoxystrobin D-5 one individualized compound I Enestroburin D-6 one individualized compound I Fenaminstrobin D-7 one individualized compound I Fenoxystrobin/Flufenoxystrobin D-8 one individualized compound I Fluoxastrobin D-9 one individualized compound I Kresoxim-methyl D-10 one individualized compound I Metominostrobin D-11 one individualized compound I Orysastrobin D-12 one individualized compound I Picoxystrobin D-13 one individualized compound I Pyraclostrobin D-14 one individualized compound I Pyrametostrobin D-15 one individualized compound I Pyraoxystrobin D-16 one individualized compound I Pyribencarb D-17 one individualized compound I Trifloxystrobin D-18 one individualized compound I Triclopyricarb/Chlorodincarb D-19 one individualized compound I 2-[2-(2,5-dimethyl-phenoxymethyl)- phenyl]-3-methoxy-acrylic acid methyl ester D-20 one individualized compound I 2-(2-(3-(2,6-dichlorophenyl)-1-methyl- allylideneaminooxymethyl)-phenyl)- 2-methoxyimino-N-methyl-acetamide D-21 one individualized compound I Benalaxyl D-22 one individualized compound I Benalaxyl-M D-23 one individualized compound I Benodanil D-24 one individualized compound I Benzovindiflupyr D-25 one individualized compound I Bixafen D-26 one individualized compound I Boscalid D-27 one individualized compound I Carboxin D-28 one individualized compound I Fenfuram D-29 one individualized compound I Fenhexamid D-30 one individualized compound I Flutolanil D-31 one individualized compound I Fluxapyroxad D-32 one individualized compound I Furametpyr D-33 one individualized compound I Isopyrazam D-34 one individualized compound I Isotianil D-35 one individualized compound I Kiralaxyl D-36 one individualized compound I Mepronil D-37 one individualized compound I Metalaxyl D-38 one individualized compound I Metalaxyl-M D-39 one individualized compound I Ofurace D-40 one individualized compound I Oxadixyl D-41 one individualized compound I Oxycarboxin D-42 one individualized compound I Penflufen D-43 one individualized compound I Penthiopyrad D-44 one individualized compound I Sedaxane D-45 one individualized compound I Tecloftalam D-46 one individualized compound I Thifluzamide D-47 one individualized compound I Tiadinil D-48 one individualized compound I 2-Amino-4-methyl-thiazole-5- carboxylic acid anilide D-49 one individualized compound I N-(4′-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1H-pyrazole- 4-carboxamide D-50 one individualized compound I N-(2-(1,3,3-trimethyl-butyl)-phenyl)- 1,3-dimethyl-5-fluoro-1H-pyrazole- 4-carboxamide D-51 one individualized compound I 3-(difluoromethyl)-1-methyl-N-(1,1,3-tri- methylindan-4-yl)pyrazole-4-carbox- amide D-52 one individualized compound I 3-(trifluoromethyl)-1-methyl-N-(1,1,3-tri- methylindan-4-yl)pyrazole-4-carbox- amide D-53 one individualized compound I 1,3-dimethyl-N-(1,1,3-trimethylindan- 4-yl)pyrazole-4-carboxamide D-54 one individualized compound I 3-(trifluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide D-55 one individualized compound I 3-(difluoromethyl)-1,5-dimethyl- N-(1,1,3-trimethylindan-4-yl)pyrazole- 4-carboxamide D-56 one individualized compound I 1,3,5-trimethyl-N-(1,1,3-trimethylindan- 4-yl)pyrazole-4-carboxamide D-57 one individualized compound I Dimethomorph D-58 one individualized compound I Flumorph D-59 one individualized compound I Pyrimorph D-60 one individualized compound I Flumetover D-61 one individualized compound I Fluopicolide D-62 one individualized compound I Fluopyram D-63 one individualized compound I Zoxamide D-64 one individualized compound I Carpropamid D-65 one individualized compound I Diclocymet D-66 one individualized compound I Mandipropamid D-67 one individualized compound I Oxytetracyclin D-68 one individualized compound I Silthiofam D-69 one individualized compound I N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide D-70 one individualized compound I Azaconazole D-71 one individualized compound I Bitertanol D-72 one individualized compound I Bromuconazole D-73 one individualized compound I Cyproconazole D-74 one individualized compound I Difenoconazole D-75 one individualized compound I Diniconazole D-76 one individualized compound I Diniconazole-M D-77 one individualized compound I Epoxiconazole D-78 one individualized compound I Fenbuconazole D-79 one individualized compound I Fluquinconazole D-80 one individualized compound I Flusilazole D-81 one individualized compound I Flutriafol D-82 one individualized compound I Hexaconazol D-83 one individualized compound I Imibenconazole D-84 one individualized compound I Ipconazole D-85 one individualized compound I Metconazole D-86 one individualized compound I Myclobutanil D-87 one individualized compound I Oxpoconazol D-88 one individualized compound I Paclobutrazol D-89 one individualized compound I Penconazole D-90 one individualized compound I Propiconazole D-91 one individualized compound I Prothioconazole D-92 one individualized compound I Simeconazole D-93 one individualized compound I Tebuconazole D-94 one individualized compound I Tetraconazole D-95 one individualized compound I Triadimefon D-96 one individualized compound I Triadimenol D-97 one individualized compound I Triticonazole D-98 one individualized compound I Uniconazole D-99 one individualized compound I 1-[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]- 5-thiocyanato-1H-[1,2,4]triazole, D-100 one individualized compound I 2-[rel-(2S;3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1,2,4]triazole-3-thiol D-101 one individualized compound I Cyazofamid D-102 one individualized compound I Amisulbrom D-103 one individualized compound I Imazalil D-104 one individualized compound I Imazalil-sulfate D-105 one individualized compound I Pefurazoate D-106 one individualized compound I Prochloraz D-107 one individualized compound I Triflumizole D-108 one individualized compound I Benomyl D-109 one individualized compound I Carbendazim D-110 one individualized compound I Fuberidazole D-111 one individualized compound I Thiabendazole D-112 one individualized compound I Ethaboxam D-113 one individualized compound I Etridiazole D-114 one individualized compound I Hymexazole D-115 one individualized compound I 2-(4-Chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2- prop-2-yn-yloxy-acetamide D-116 one individualized compound I Fluazinam D-117 one individualized compound I Pyrifenox D-118 one individualized compound I 3-[5-(4-Chloro-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine (Pyrisoxazole) D-119 one individualized compound I 3-[5-(4-Methyl-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine D-120 one individualized compound I Bupirimate D-121 one individualized compound I Cyprodinil D-122 one individualized compound I 5-Fluorocytosine D-123 one individualized compound I 5-Fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine D-124 one individualized compound I 5-Fluoro-2-(4-fluorophenylmethoxy)- pyrimidin-4-amine D-125 one individualized compound I Diflumetorim D-126 one individualized compound I (5,8-Difluoroquinazolin-4-yl)-{2-[2-fluoro- 4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]-ethyl}-amine D-127 one individualized compound I Fenarimol D-128 one individualized compound I Ferimzone D-129 one individualized compound I Mepanipyrim D-130 one individualized compound I Nitrapyrin D-131 one individualized compound I Nuarimol D-132 one individualized compound I Pyrimethanil D-133 one individualized compound I Triforine D-134 one individualized compound I Fenpiclonil D-135 one individualized compound I Fludioxonil D-136 one individualized compound I Aldimorph D-137 one individualized compound I Dodemorph D-138 one individualized compound I Dodemorph-acetate D-139 one individualized compound I Fenpropimorph D-140 one individualized compound I Tridemorph D-141 one individualized compound I Fenpropidin D-142 one individualized compound I Fluoroimid D-143 one individualized compound I Iprodione D-144 one individualized compound I Procymidone D-145 one individualized compound I Vinclozolin D-146 one individualized compound I Famoxadone D-147 one individualized compound I Fenamidone D-148 one individualized compound I Flutianil D-149 one individualized compound I Octhilinone D-150 one individualized compound I Probenazole D-151 one individualized compound I Fenpyrazamine D-152 one individualized compound I Acibenzolar-S-methyl D-153 one individualized compound I Ametoctradin D-154 one individualized compound I Amisulbrom D-155 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-iso- butyryloxymethoxy-4-methoxypyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo- [1,5]dioxonan-7-yl] 2-methylpropanoate D-156 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy- 4-methoxy-pyridine-2-carbonyl)amino]- 6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate D-157 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3- (acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate D-158 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[(3- isobutoxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate D-159 one individualized compound I [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3- benzodioxol-5-ylmethoxy)-4-methoxy-pyri- dine-2-carbonyl]amino]-6-methyl-4,9- dioxo-1,5-dioxonan-7-yl] 2-methylpropanoate D-160 one individualized compound I (3S,6S,7R,8R)-3-[[(3-hydroxy-4- methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)- 1,5-dioxonan-7-yl 2-methylpropanoate D-161 one individualized compound I Anilazin D-162 one individualized compound I Blasticidin-S D-163 one individualized compound I Captafol D-164 one individualized compound I Captan D-165 one individualized compound I Chinomethionat D-166 one individualized compound I Dazomet D-167 one individualized compound I Debacarb D-168 one individualized compound I Diclomezine D-169 one individualized compound I Difenzoquat, D-170 one individualized compound I Difenzoquat-methylsulfate D-171 one individualized compound I Fenoxanil D-172 one individualized compound I Folpet D-173 one individualized compound I Oxolinsäure D-174 one individualized compound I Piperalin D-175 one individualized compound I Proquinazid D-176 one individualized compound I Pyroquilon D-177 one individualized compound I Quinoxyfen D-178 one individualized compound I Triazoxid D-179 one individualized compound I Tricyclazole D-180 one individualized compound I 2-Butoxy-6-iodo-3-propyl-chromen-4- one D-181 one individualized compound I 5-Chloro-1-(4,6-dimethoxy-pyrimidin-2- yl)-2-methyl-1H-benzoimidazole D-182 one individualized compound I 5-Chloro-7-(4-methyl-piperidin-1-yl)- 6-(2,4,6-trifluoro-phenyl)-[1,2,4]tri- azolo[1,5-a]pyrimidine D-183 one individualized compound I Ferbam D-184 one individualized compound I Mancozeb D-185 one individualized compound I Maneb D-186 one individualized compound I Metam D-187 one individualized compound I Methasulphocarb D-188 one individualized compound I Metiram D-189 one individualized compound I Propineb D-190 one individualized compound I Thiram D-191 one individualized compound I Zineb D-192 one individualized compound I Ziram D-193 one individualized compound I Diethofencarb D-194 one individualized compound I Benthiavalicarb D-195 one individualized compound I Iprovalicarb D-196 one individualized compound I Propamocarb D-197 one individualized compound I Propamocarb hydrochlorid D-198 one individualized compound I Valifenalate D-199 one individualized compound I N-(1-(1-(4-cyanophenyl)ethane- sulfonyl)-but-2-yl) carbamic acid- (4-fluorophenyl) ester D-200 one individualized compound I Dodine D-201 one individualized compound I Dodine free base D-202 one individualized compound I Guazatine D-203 one individualized compound I Guazatine-acetate D-204 one individualized compound I Iminoctadine D-205 one individualized compound I Iminoctadine-triacetate D-206 one individualized compound I Iminoctadine-tris(albesilate) D-207 one individualized compound I Kasugamycin D-208 one individualized compound I Kasugamycin-hydrochloride-hydrate D-209 one individualized compound I Polyoxine D-210 one individualized compound I Streptomycin D-211 one individualized compound I Validamycin A D-212 one individualized compound I Binapacryl D-213 one individualized compound I Dicloran D-214 one individualized compound I Dinobuton D-215 one individualized compound I Dinocap D-216 one individualized compound I Nitrothal-isopropyl D-217 one individualized compound I Tecnazen D-218 one individualized compound I Fentin salts D-219 one individualized compound I Dithianon D-220 one individualized compound I 2,6-dimethyl-1H,5H-[1,4]dithiino [2,3-c:5,6-c′]dipyrrole- 1,3,5,7(2H,6H)-tetraone D-221 one individualized compound I Isoprothiolane D-222 one individualized compound I Edifenphos D-223 one individualized compound I Fosetyl, Fosetyl-aluminium D-224 one individualized compound I Iprobenfos D-225 one individualized compound I Phosphorous acid (H₃PO₃) and derivatives D-226 one individualized compound I Pyrazophos D-227 one individualized compound I Tolclofos-methyl D-228 one individualized compound I Chlorothalonil D-229 one individualized compound I Dichlofluanid D-230 one individualized compound I Dichlorophen D-231 one individualized compound I Flusulfamide D-232 one individualized compound I Hexachlorbenzene D-233 one individualized compound I Pencycuron D-234 one individualized compound I Pentachlorophenol and salts D-235 one individualized compound I Phthalide D-236 one individualized compound I Quintozene D-237 one individualized compound I Thiophanate Methyl D-238 one individualized compound I Tolylfluanid D-239 one individualized compound I N-(4-chloro-2-nitro-phenyl)-N-ethyl- 4-methyl-benzenesulfonamide D-240 one individualized compound I Bordeaux mixture D-241 one individualized compound I Copper acetate D-242 one individualized compound I Copper hydroxide D-243 one individualized compound I Copper oxychloride D-244 one individualized compound I basic Copper sulfate D-245 one individualized compound I Sulfur D-246 one individualized compound I Biphenyl D-247 one individualized compound I Bronopol D-248 one individualized compound I Cyflufenamid D-249 one individualized compound I Cymoxanil D-250 one individualized compound I Diphenylamin D-251 one individualized compound I Metrafenone D-252 one individualized compound I Pyriofenone D-253 one individualized compound I Mildiomycin D-254 one individualized compound I Oxin-copper D-255 one individualized compound I Oxathiapiprolin D-256 one individualized compound I Prohexadione calcium D-257 one individualized compound I Spiroxamine D-258 one individualized compound I Tebufloquin D-259 one individualized compound I Tolylfluanid D-260 one individualized compound I N-(Cyclopropylmethoxyimino-(6- difluoromethoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide D-261 one individualized compound I N′-(4-(4-chloro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine D-262 one individualized compound I N′-(4-(4-fluoro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine D-263 one individualized compound I N′-(2-methyl-5-trifluoromethyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine D-264 one individualized compound I N′-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine D-265 one individualized compound I Methoxy-acetic acid 6-tert-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester D-266 one individualized compound I Bacillus subtilis NRRL No. B-21661 D-267 one individualized compound I Bacillus pumilus NRRL No. B-30087 D-268 one individualized compound I Ulocladium oudemansii D-269 one individualized compound I Carbaryl D-270 one individualized compound I Carbofuran D-271 one individualized compound I Carbosulfan D-272 one individualized compound I Methomylthiodicarb D-273 one individualized compound I Bifenthrin D-274 one individualized compound I Cyfluthrin D-275 one individualized compound I Cypermethrin D-276 one individualized compound I alpha-Cypermethrin D-277 one individualized compound I zeta-Cypermethrin D-278 one individualized compound I Deltamethrin D-279 one individualized compound I Esfenvalerate D-280 one individualized compound I Lambda-cyhalothrin D-281 one individualized compound I Permethrin D-282 one individualized compound I Tefluthrin D-283 one individualized compound I Diflubenzuron D-284 one individualized compound I Flufenoxuron D-285 one individualized compound I Lufenuron D-286 one individualized compound I Teflubenzuron D-287 one individualized compound I Spirotetramate D-288 one individualized compound I Clothianidin D-289 one individualized compound I Dinotefuran D-290 one individualized compound I Imidacloprid D-291 one individualized compound I Thiamethoxam D-292 one individualized compound I Flupyradifurone D-293 one individualized compound I Acetamiprid D-294 one individualized compound I Thiacloprid D-295 one individualized compound I Endosulfan D-296 one individualized compound I Fipronil D-297 one individualized compound I Abamectin D-298 one individualized compound I Emamectin D-299 one individualized compound I Spinosad D-300 one individualized compound I Spinetoram D-301 one individualized compound I Hydramethylnon D-302 one individualized compound I Chlorfenapyr D-303 one individualized compound I Fenbutatin oxide D-304 one individualized compound I Indoxacarb D-305 one individualized compound I Metaflumizone D-306 one individualized compound I Flonicamid D-307 one individualized compound I Lubendiamide D-308 one individualized compound I Chlorantraniliprole D-309 one individualized compound I Cyazypyr (HGW86) D-310 one individualized compound I Cyflumetofen D-311 one individualized compound I Acetochlor D-312 one individualized compound I Dimethenamid D-313 one individualized compound I metolachlor D-314 one individualized compound I Metazachlor D-315 one individualized compound I Glyphosate D-316 one individualized compound I Glufosinate D-317 one individualized compound I Sulfosate D-318 one individualized compound I Clodinafop D-319 one individualized compound I Fenoxaprop D-320 one individualized compound I Fluazifop D-321 one individualized compound I Haloxyfop D-322 one individualized compound I Paraquat D-323 one individualized compound I Phenmedipham D-324 one individualized compound I Clethodim D-325 one individualized compound I Cycloxydim D-326 one individualized compound I Profoxydim D-327 one individualized compound I Sethoxydim D-328 one individualized compound I Tepraloxydim D-329 one individualized compound I Pendimethalin D-330 one individualized compound I Prodiamine D-331 one individualized compound I Trifluralin D-332 one individualized compound I Acifluorfen D-333 one individualized compound I Bromoxynil D-334 one individualized compound I Imazamethabenz D-335 one individualized compound I Imazamox D-336 one individualized compound I Imazapic D-337 one individualized compound I Imazapyr D-338 one individualized compound I Imazaquin D-339 one individualized compound I Imazethapyr D-340 one individualized compound I 2,4-Dichlorophenoxyacetic acid (2,4-D) D-341 one individualized compound I Chloridazon D-342 one individualized compound I Clopyralid D-343 one individualized compound I Fluroxypyr D-344 one individualized compound I Picloram D-345 one individualized compound I Picolinafen D-346 one individualized compound I Bensulfuron D-347 one individualized compound I Chlorimuron-ethyl D-348 one individualized compound I Cyclosulfamuron D-349 one individualized compound I Iodosulfuron D-350 one individualized compound I Mesosulfuron D-351 one individualized compound I Metsulfuron-methyl D-352 one individualized compound I Nicosulfuron D-353 one individualized compound I Rimsulfuron D-354 one individualized compound I Triflusulfuron D-355 one individualized compound I Atrazine D-356 one individualized compound I Hexazinone D-357 one individualized compound I Diuron D-358 one individualized compound I Florasulam D-359 one individualized compound I Pyroxasulfone D-360 one individualized compound I Bentazone D-361 one individualized compound I Cinidon-ethyl D-362 one individualized compound I Cinmethylin D-363 one individualized compound I Dicamba D-364 one individualized compound I Diflufenzopyr D-365 one individualized compound I Quinclorac D-366 one individualized compound I Quinmerac D-367 one individualized compound I Mesotrione D-368 one individualized compound I Saflufenacil D-369 one individualized compound I Topramezone D-370 one individualized compound I 1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS, 12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]- 1,3,4,4a,5,6,6a,12,12a,12b-deca-hydro- 12-hydroxy-4,6a,12b-trimethyl- 11-oxo-9-(3-pyridinyl)-2H,11H-naph- tho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester

The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S. Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 11/028,657).

The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e.g. by the means given for the compositions of compounds I.

Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.

The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds I, respectively.

I. SYNTHESIS EXAMPLES

With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain further compounds I. The compounds produced in this manner are listed in Table V below including corresponding physical data. 2-(2-Chloro-4-hydroxyphenyl)ethylamine-tert-butylcarbamate was prepared as described in WO 2004026305 A1. 2-(2-Fluoro-4-methoxyphenyl)ethylamine hydrochloride was prepared from 2-fluoro-4-methoxybenzaldehyde as described in US 20110054173 A1. 2-(3-Methoxy-4-hydroxyphenyl)ethylamine-tert-butylcarbamate was prepared according to literature precedents in Bioorganic & Medicinal Chemistry (2011), 19(2), 783-788 and in European Journal of Medicinal Chemistry (2008), 43(6), 1160-1170. 6-Dichloro-5-pyrimidinecarboxylic acid methyl ester was prepared from 4,6-dihydroxypyrimidine as described in Journal of Medicinal Chemistry (2010), 53(13), 5012-5024.

Example 1 Preparation of 2-(2-fluoro-4-hydroxyphenyl)ethylamine-tert-butyl carbamate

2-(2-Fluoro-4-methoxyphenyl)ethylamine hydrochloride (270 g, 1.6 mol) was carefully added portionwise to 48% HBr (1.5 L) and stirred for 4 h at 140° C. The reaction solution was reduced in vacuo, then acetonitrile (1 L) was added to the residue and was evaporated to dryness. The crude product was stirred in diisopropylether and recovered by filtration to afford 222 g (940 mmol, 59%) of desired phenol. The purified phenol was dissolved in dichloromethane (DCM, 1.5 L) to which was added triethylamine (275 mL), tert-butyloxycarbonyl anhydride (215 g, 990 mmol) in a solution of DCM (500 mL), and was stirred for 30 min at room temperature. The reaction solution was washed with water, dried over Na₂SO₄ and then concentrated in vacuo. The residue was purified by flash silica column chromatography (4:1 cyclohexane:MTBE) to afford 220 g (860 mmol, 92%) of 2-(2-Fluoro-4-hydroxyphenyl)ethylamine-tert-butyl carbamate.

Example 2 Preparation of 2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine hydrochloride

To a solution of N-tert-butyloxy-carbonyl-protected tyramine (130 g, 550 mmol), potassium carbonate (76 g, 550 mmol) and catalytic amounts of potassium iodide in N-methyl-2-pyrrolidone (NMP, 400 mL) that was stirred for 10 minutes at room temperature was added 4-chloro-2-trifluoromethylpyridine (100 g, 550 mmol). The reaction mixture was then heated to 160° C. for 6 h, cooled, poured into water and extracted with methyl tert-butylether (MTBE, 3×). The combined organic layers were washed with succesivly with 3 N NaOH and water, dried over Na₂SO₄, and reduced in vacuo. The crude residue was purified by flash silica gel column chromatography to afford a 48% (102 g, 265 mmol) yield of N-tert-butyloxycarbonyl-protected 2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine. To a solution of this material in dioxane (200 mL) was added 4 M HCl in dioxane (250 mL). The solution was left overnight to stir at room temperature, which resulted in precipitation of 2-[4-[[2-(trifluoromethyl)-4-pyridyl]oxy]phenyl]ethanamine. The reaction solution was evaporated and the residue was stirred with pentane and filtered to provide 100% (37 g, 104 mmol) of the desired amine hydrochloride.

Example 3 Preparation of 6-chloro-N-[2-[4-(6-chloro-5-methoxy-pyrimidin-4-yl)oxyphenyl]ethyl]-5-methoxy-pyrimidin-4-amine (V-17)

To a solution of 4-hydroxyphenylethylamine hydrochloride (300 mg) in N,N-dimethyl formamide (DMF, 5 mL) was added diisopropylethylamine (355 mg, 2 equiv.). The solution was stirred for 5 min before the addition of 4,6-dichloro-5-methoxypyrimidine (249 mg, 1 equiv.). The reaction mixture was then stirred for 16 h at room temperature before it was concentrated in vacuo. The residue was dissolved in DMF (10 mL) and was stirred with sodium hydride (66 mg, 2.2 equiv.) for 20 min at room temperature. Another portion of 4,6-dichloro-5-methoxypyrimidine (269 mg, 1.2 equiv.) was introduced into the reaction mixture, which was then left to stir at room temperature for 48 h. The DMF was then removed in vacuo and the product was purified by flash silica column chromatography to afford 178 mg (31% yield) of the product as a white solid.

Example 4 Preparation of 6-chloro-N-[2-[2-fluoro-4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]ethyl]-5-methoxy-pyrimidin-4-amine (V-3)

To a solution of 2-[2-fluoro-4-[[4-(trifluoromethyl)-2-pyridyl]oxy]phenyl]ethanamine hydrochloride (378 mg, 1 mmol) in N-methyl-2-pyrrolidone (5 mL) was added diisopropylethylamine (0.4 mL, 2.3 mmol). The solution was stirred for 5 min at room temperature at which time 4,6-dichloro-5-methylpyrimidine (150 mg, 0.8 mmol) was added. The reaction mixture was stirred at 80° C. overnight then allowed to cool to room temperature. Water was added and was extracted with MTBE (3×). The combined organic layers were washed with water, dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by flash silica column chromatography to provide 330 mg (0.80 mmol, 84%) of the light yellow solid product.

The compounds listed in Table V have been prepared in an analogous manner.

TABLE V Compounds V-1 to V-49 of formula I.A as defined above and wherein R¹ and R² in each case are hydrogen. ex. HPLC m.p. no R^(a2) R^(a5) R^(a6) Het R X (R^(b))_(n)* R_(t) (min) (° C.) V-1 H Cl Cl H-1 H —CH₂— n = 0 3.999 89 V-2 H H Cl H-1 H —CH₂— n = 0 3.568 135 V-3 H Me Cl H-1 H —CH₂— o-F; n = 1 1.289 121 V-4 H OMe Cl H-1 H —CH₂— o-F; n = 1 1.297 95 V-5 H COOMe Cl H-2 H —CH₂— n = 0 1.316 V-6 H COOMe Cl H-2 H —CH₂— o-F; n = 1 1.326 112 V-7 H Cl Cl H-1 H —CH₂— o-F; n = 1 1.364 97 V-8 H Cl Cl H-1 H —CH₂— m-OMe; n = 1 1.35 V-9 H Me Cl H-2 H —CH₂— o-F; n = 1 1.221 V-10 H F Cl H-1 H —CH₂— o-F; n = 1 1.332 142 V-11 H F Cl H-2 H —CH₂— o-F; n = 1 1.278 116 V-12 H Br F H-1 H —CH₂— o-F; n = 1 1.361 V-13 H Me Cl H-1 H —CH₂— m-Cl; n = 1 1.317 120 V-14 H OMe Cl H-1 Me —CH₂— o-F; n = 1 1.373 V-15 H CN Cl H-1 H —CH₂— n = 0 1.34 105 V-16 H OMe Cl H-1 H —CH₂— m-OMe; n = 1 1.231 106 V-17 H OMe Cl H-28 H —CH₂— n = 0 1.157 123 V-18 H OMe Cl H-7 H —CH₂— n = 0 1.11 125 V-19 H OMe Cl H-1 H —CH₂— n = 0 1.27 V-20 H OMe Cl H-2 H —CH₂— m-OMe; n = 1 1.21 V-21 H OMe Cl H-2 H —CH₂— n = 0 1.22 V-22 H OMe Cl H-6 H —CH₂— n = 0 1.1 105 V-23 H OMe Cl H-1 H —CH(CH₂OH)— n = 0 1.169 V-24 H Me Cl H-1 H —CH(CH₂OH)— n = 0 1.142 V-25 Me Cl Cl H-1 H —CH₂— o-F; n = 1 1.432 108 V-26 Me Me Cl H-1 H —CH₂— o-F; n = 1 1.172 V-27 H OMe Cl H-1 Me —CH₂— o-F, n = 1 1.373 V-28 H Me Cl H-30 H —CH₂— n = 0 1.173 162 V-29 H CN Cl H-1 H —CH₂— o-F; n = 1 1.34 184 V-30 H Cl Cl H-2 H —CH(CH₃)— n = 0 1.36 150 V-31 H Br Cl H-1 H —CH₂— o-F; n = 1 1.403 V-32 H COOMe Cl H-1 H —CH₂— o-F; n = 1 1.37 V-33 Cl Cl Cl H-1 H —CH₂— o-F; n = 1 1.468 V-34 H Et Cl H-1 H —CH₂— m-F; n = 1 1.338 V-35 H Et Cl H-2 H —CH₂— m-F; n = 1 1.294 130 V-36 H Br Cl H-2 H —CH₂— o-F; n = 1 1.354 132 V-37 H Me Cl H-1 H —CH₂— m-Me; n = 1 1.278 130 V-38 Me Me Cl H-2 H —CH₂— o-F; n = 1 1.140 141 V-39 Me C(CH₃)₃ Cl H-1 H —CH₂— o-F; n = 1 1.238 V-40 Me C(CH₃)₃ Cl H-2 H —CH₂— o-F; n = 1 1.199 V-41 H Et Cl 6-chloro- H —CH₂— n = 0 1.291 116 5-ethyl- pyrimidin- 4-yl V-42 NH₂ H Cl H-1 H —CH₂— o-F; n = 1 1.052 V-43 Me H Cl H-1 H —CH₂— o-F; n = 1 1.208 V-44 H Me Cl H-1 H —CH₂— m-F; n = 1 1.252 126 V-45 H Me Cl H-7 H —CH₂— n = 0 1.09 139 V-46 H Me Cl H-8 H —CH₂— n = 0 1.07 V-47 H Cl Cl H-1 H —CH(CH₂OH)— n = 0 1.228 V-48 H OMe Cl H-1 H —CH(COOMe)— n = 0 1.310 V-49 H Me Cl H-1 H —CH(CH₂OCH₃)— n = 0 1.293 87 *The position of R^(b) on the phenyl ring is defined relative to the CR¹R²-moiety bound to the phenyl ring as being in ortho (o-) or meta (m-) position. n = 0 indicates that no substituent R^(b) is present on the phenyl ring. m.p. = melting point (° C.). HPLC-MS: HPLC-column Kinetex XB C18 1.7μ (50 × 2.1 mm); eluent: acetonitrile/water + 0.1% TFA (gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray Ionisation, 80 V (positive mode).

II. BIOLOGICAL EXAMPLES FOR FUNGICIDAL ACTIVITY

The fungicidal action of the compounds I was demonstrated by the following experiments:

A. Glass House Trials

The spray solutions were prepared in several steps: The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml. Water was then added to total volume of 100 ml.

This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.

After the final cultivation period, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Use Example 1 Protective Control of Soy Bean Rust on Soy Beans Caused by Phakopsora Pachyrhizi

Leaves of pot-grown soybean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 1 day in a greenhouse chamber at 23 to 27° C. and a relative humidity between 60 and 80%. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20-24° C. for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23 to 27° C. and a relative humidity between 60 and 80%.

In this test, the plants which had been treated with 250 ppm of the active compound V-1, V-2, V-3, V-4, V-5, V-8, V-10, V-11, V-14, V-16, V-17, V-23, V-26, V-27, V-31, V-32, V-34, V-37, V-42, V-43, V-44, V-47 or V-48 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 94% diseased leaf area.

Use Example 2 Preventative Control of Brown Rust on Wheat Caused by Puccinia Recondite

The first two developed leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The next day the plants were inoculated with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99% and 20 to 24° C. for 24 h. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 20 to 24° C. and a relative humidity between 65 and 70%.

In this test, the plants which had been treated with 250 ppm of the active compound V-1, V-2, V-4, V-5, V-7, V-10, V-11, V-14, V-15, V-25, V-26, V-27, V-35 or V-38 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 86% diseased leaf area.

Use Example 3 Preventative Control of Leaf Blotch on Wheat Caused by Septoria tritici

Leaves of pot-grown wheat seedling were sprayed to run-off with an aqueous suspension of the active compound or their mixture, prepared as described. The plants were allowed to air-dry. At the following day the plants were inoculated with an aqueous spore suspension of Septoria tritici. Then the trial plants were immediately transferred to a humid chamber at 18 to 22° C. and a relative humidity close to 100%. After 4 days the plants were transferred to a chamber with 18 to 22° C. and a relative humidity close to 70% and kept there for 4 weeks.

In this test, the plants which had been treated with 250 ppm of the active compound V-1, V-2, V-3, V-4, V-5, V-6, V-7, V-9, V-11, V-12, V-13, V-14, V-15, V-16, V-26, V-27, V-29, V-30, V-31, V-32, V-33, V-36, V-37, V-39 or V-40 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 93% diseased leaf area.

Use Example 4 Control of Late Blight on Tomatoes Caused by Phytophthora infestans

Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber and kept for 6 days at 18 to 20° C. and a relative humidity close to 100%.

In this test, the plants which had been treated with 250 ppm of the active compound V-3, V-4, V-6, V-9, V-14, V-15, V-16, V-17, V-18, V-19, V-20, V-21, V-22, V-23, V-24, V-26, V-27, V-28, V-29, V-46 or V-47 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 80% diseased leaf area.

Use Example 5 Control of Late Blight on Tomatoes Caused by Phytophthora infestans

Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. Seven days later the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber and kept for 6 days at 18 to 20° C. and a relative humidity close to 100%.

In this test, the plants which had been treated with 250 ppm of the active compound V-4, V-15, V-17, V-23, V-28, V-41, V-45 or V-49 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 60% diseased leaf area.

Use Example 6 Preventative Fungicidal Control of Botiytis Cinerea on Leaves of Green Pepper

Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with a aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber and kept for 5 days at 22 to 24° C. and a relative humidity close to 100%.

In this test, the plants which had been treated with 250 ppm of the active compound V-2, V-4, V-12, V-13, V-15 or V-40 showed a diseased leaf area of at most 20%, whereas the untreated plants showed 89% diseased leaf area. 

We claim:
 1. A compound of formula I

wherein: R^(a2), R^(a5) independently of each other, are hydrogen, halogen, CN, NO₂, OH, SH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkenyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyloxy, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, NR^(A)R^(B), C(═O)R′, C(═NOR″)R′″ or —C(═NH)—O—R′″; R^(A), R^(B) independently of each other are hydrogen, C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, phenyl, benzyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkenyl or —C(═O)—R′; R′ is hydrogen, OH, NH₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino or di(C₁-C₄-alkyl)amino; R″ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl or C₁-C₄-alkoxy-C₁-C₄-alkyl; R′″ is hydrogen or C₁-C₄-alkyl; R^(a6) is halogen; R is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, CN, CH₂CN, NR^(A)R^(B) or CH₂—O—C(═O)R′; R¹, R² independently of each other are hydrogen, halogen, CN, OH, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B), C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or two radicals R¹ and R² that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of the abovementioned cycles may be respectively replaced by one or two C═O or C═S groups; X is a divalent group selected from —CR³R⁴—, —C(═NR^(D))— and —C(═NOR^(D))—, wherein R^(D) is hydrogen or C₁-C₄-alkyl, and wherein R³ and R⁴ independently of each other are hydrogen, CN, C₁-C₄-hydroxyalkyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, C₃-C₈-cycloalkyloxy, NR^(A)R^(B), C(═O)R′, C(═NOR″)R′″, —C(═NH)—O—R′″ or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1, 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, (C₁-C₄-alkoxy)carbonyl and di(C₁-C₄-alkyl)aminocarbonyl, or two radicals R³ and R⁴ that are bound to the same carbon atom form together with said carbon atom a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered carbocycle or a saturated or partially unsaturated 3-, 4-, 5-, 6-, or 7-membered heterocycle, wherein the ring member atoms of the abovementioned heterocycle include beside carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the abovementioned cycle is unsubstituted or carries 1, 2, 3 or 4 substituents selected from halogen, CN, OH, SH, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio; and one or two CH₂ groups of the abovementioned cycles may be respectively replaced by one or two C(═O) or C(═S) groups; n indicates the number of substituents R^(b) on the phenyl ring and n is 0, 1, 2, 3 or 4; R^(b) is halogen, CN, NO₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, NR^(A)R^(B), C(═NOR″)R′″ or —C(═NH)—O—R′″, it being possible for n=2, 3 or 4 that R^(b) are identical or different; Het is a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups R^(c): R^(c) is halogen, CN, NO₂, NH₂, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylamino, di(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-haloalkoxy-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C(═O)R′, C(═NOR″)R′″, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkyl-C₁-C₄-alkyl, phenyl, phenoxy, phenoxy-C₁-C₄-alkyl or a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1, 2, 3 or 4 identical or different substituents R^(d): R^(d) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; or two radicals R^(c) that are bound to adjacent ring member atoms of the Het group form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups R^(e): R^(e) is halogen, CN, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; and the N-oxides and the agriculturally acceptable salts of the compounds of formula I.
 2. The compound according to claim 1, wherein R^(a2) and R^(a5) independently of each other are halogen, CN, C₁-C₄-alkyl, C₁-C₄-alkoxy, haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy or (C₁-C₄-alkoxy)-carbonyl, and it being possible that one of both, R^(a2) or R^(a5) can in addition be hydrogen.
 3. The compound according to claim 1, wherein R^(a6) is chlorine or fluorine.
 4. The compound according to claim 1, wherein X is —CH₂—.
 5. The compound according to claim 1, wherein R¹ and R² are both hydrogen.
 6. The compound according to claim 1, wherein Het is selected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridin-2-yl, pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.
 7. The compound according to claim 1, wherein Het carries 1 or 2 radicals R^(c) which are selected from F, Cl, Br, CN, C₁-C₂-alkylsulfonyl, C₁-C₂-alkoxycarbonyl, aminocarbonyl, C₁-C₂-alkylaminocarbonyl, di(C₁-C₂-alkyl)aminocarbonyl, C₁-C₂-alkoxy, CF₃, CHF₂, OCF₃ and OCHF₂.
 8. The compound according to claim 1, wherein R is hydrogen.
 9. A process for preparing the compound of claim 1, wherein X is —CR³R⁴—, which comprises reacting a compound of formula II

wherein R^(a2), R^(a5) and R^(a6) are as defined in claim 1, Hal is fluorine, chlorine or bromine, with a compound of formula III

wherein R, R¹, R², R^(b), n and Het are as defined in claim 1 and X is —CR³R⁴— as defined in claim 1 in the presence of a base or a catalyst or a combination of a base and a catalyst in a solvent.
 10. An agrochemical composition which comprises an auxiliary and at least one compound of claim
 1. 11. The agrochemical composition according to claim 10 comprising at least one further active substance.
 12. A method for combating phytopathogenic harmful fungi, which method comprises treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of claim
 1. 13. The method of claim 12, wherein, in the compound of formula I, R^(a2) and R^(a5) independently of each other are halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkoxy or (C₁-C₄-alkoxy)-carbonyl, and it being possible that one of both, R^(a2) or R^(a5) can in addition be hydrogen.
 14. The method of claim 12, wherein, in the compound of formula I, R^(a6) is chlorine or fluorine.
 15. The method of claim 12, wherein, in the compound of formula I, X is —CH₂—.
 16. The method of claim 12, wherein, in the compound of formula I, R¹ and R² are both hydrogen.
 17. The method of claim 12, wherein, in the compound of formula I, Het is selected from the group consisting of pyrimidin-2-yl, pyrimidin-3-yl, pyrimidin-4-yl, pyridine-2-yl, pyridin-3-yl, thiazol-2-yl, pyrazin-2-yl, pyridazin-3-yl, 1,3,5-triazin-2-yl, and 1,2,4-triazin-3-yl.
 18. The method of claim 12, wherein, in the compound of formula I, Het carries 1 or 2 radicals R^(c) which are selected from F, Cl, Br, CN, C₁-C₂-alkylsulfonyl, C₁-C₂-alkoxycarbonyl, aminocarbonyl, C₁-C₂-alkylaminocarbonyl, di(C₁-C₂-alkyl)aminocarbonyl, C₁-C₂-alkoxy, CF₃, CHF₂, OCF₃ and OCHF₂.
 19. The method of claim 12, wherein, in the compound of formula I, R is hydrogen. 